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1.
Molecules ; 29(9)2024 Apr 27.
Artigo em Inglês | MEDLINE | ID: mdl-38731506

RESUMO

The mechanism of ammonia formation during the pyrolysis of proteins in biomass is currently unclear. To further investigate this issue, this study employed the AMS 2023.104 software to select proteins (actual proteins) as the model compounds and the amino acids contained within them (assembled amino acids) as the comparative models. ReaxFF molecular dynamics simulations were conducted to explore the nitrogen transformation and NH3 generation mechanisms in three-phase products (char, tar, and gas) during protein pyrolysis. The research results revealed several key findings. Regardless of whether the model compounds are actual proteins or assembled amino acids, NH3 is the primary nitrogen-containing product during pyrolysis. However, as the temperature rises to higher levels, such as 2000 K and 2500 K, the amount of NH3 decreases significantly in the later stages of pyrolysis, indicating that it is being converted into other nitrogen-bearing species, such as HCN and N2. Simultaneously, we also observed significant differences between the pyrolysis processes of actual proteins and assembled amino acids. Notably, at 2000 K, the amount of NH3 generated from the pyrolysis of assembled amino acids was twice that of actual proteins. This discrepancy mainly stems from the inherent structural differences between proteins and amino acids. In proteins, nitrogen is predominantly present in a network-like structure (NH-N), which shields it from direct external exposure, thus requiring more energy for nitrogen to participate in pyrolysis reactions, making it more difficult for NH3 to form. Conversely, assembled amino acids can release NH3 through a simpler deamination process, leading to a significant increase in NH3 production during their pyrolysis.


Assuntos
Amônia , Simulação de Dinâmica Molecular , Proteínas , Pirólise , Amônia/química , Proteínas/química , Aminoácidos/química , Nitrogênio/química
2.
Water Res ; 256: 121638, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38691899

RESUMO

In this study, we investigated the recovery of nitrogen (N) and phosphorus (P) from fresh source-separated urine with a novel electrochemical cell equipped with a magnesium (Mg) anode and carbon-based gas-diffusion cathode. Recovery of P, which exists primarily as phosphate (PO43-) in urine, was achieved through pH-driven precipitation. Maximizing N recovery requires simultaneous approaches to address urea and ammonia (NH3). NH3 recovery was possible through precipitation in struvite with soluble Mg supplied by the anode. Urea was stabilized with electrochemically synthesized hydrogen peroxide (H2O2) from the cathode. H2O2 concentrations and resulting urine pH were directly proportional to the applied current density. Concomitant NH3 and PO43- precipitation as struvite and urea stabilization via H2O2 electrosynthesis was possible at lower current densities, resulting in urine pH under 9.2. Higher current densities resulted in urine pH over 9.2, yielding higher H2O2 concentrations and more consistent stabilization of urea at the expense of NH3 recovery as struvite; PO43- precipitation still occurred but in the form of calcium phosphate and magnesium phosphate solids.


Assuntos
Eletrodos , Peróxido de Hidrogênio , Magnésio , Fósforo , Ureia , Ureia/química , Fósforo/química , Magnésio/química , Peróxido de Hidrogênio/química , Concentração de Íons de Hidrogênio , Urina/química , Fosfatos/química , Estruvita/química , Amônia/química , Compostos de Magnésio/química , Nitrogênio/química , Humanos
3.
Environ Sci Technol ; 58(20): 8955-8965, 2024 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-38718175

RESUMO

The development of Fe-based catalysts for the selective catalytic reduction of NOx by NH3 (NH3-SCR of NOx) has garnered significant attention due to their exceptional SO2 resistance. However, the influence of different sulfur-containing species (e.g., ferric sulfates and ammonium sulfates) on the NH3-SCR activity of Fe-based catalysts as well as its dependence on exposed crystal facets of Fe2O3 has not been revealed. This work disclosed that nanorod-like α-Fe2O3 (Fe2O3-NR) predominantly exposing (110) facet performed better than nanosheet-like α-Fe2O3 (Fe2O3-NS) predominantly exposing (001) facet in NH3-SCR reaction, due to the advantages of Fe2O3-NR in redox properties and surface acidity. Furthermore, the results of the SO2/H2O resistance test at a critical temperature of 250 °C, catalytic performance evaluations on Fe2O3-NR and Fe2O3-NS sulfated by SO2 + O2 or deposited with NH4HSO4 (ABS), and systematic characterization revealed that the reactivity of ammonium sulfates on Fe2O3 catalysts to NO(+O2) contributed to their improved catalytic performance, while ferric sulfates showed enhancing and inhibiting effects on NH3-SCR activity on Fe2O3-NR and Fe2O3-NS, respectively; despite this, Fe2O3-NR showed higher affinity for SO2 + O2. This work set a milestone in understanding the NH3-SCR reaction on Fe2O3 catalysts in the presence of SO2 from the aspect of crystal facet engineering.


Assuntos
Amônia , Catálise , Amônia/química , Dióxido de Enxofre/química , Compostos Férricos/química , Oxirredução
4.
Environ Monit Assess ; 196(6): 552, 2024 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-38755295

RESUMO

The TiO2 nanocomposite efficiency was determined under optimized conditions with activated carbon to remove ammoniacal nitrogen (NH3-N) from the leachate sample. In this work, the facile impregnation and pyrolysis synthesis method was employed to prepare the nanocomposite, and their formation was confirmed using the FESEM, FTIR, XRD, and Raman studies. In contrast, Raman phonon mode intensity ratio ID/IG increases from 2.094 to 2.311, indicating the increase of electronic conductivity and defects with the loading of TiO2 nanoparticles. The experimental optimal conditions for achieving maximum NH3-N removal of 75.8% were found to be a pH of 7, an adsorbent mass of 1.75 mg/L, and a temperature of 30 °C, with a corresponding time of 160 min. The experimental data were effectively fitted with several isotherms (Freundlich, Hill, Khan, Redlich-Peterson, Toth, and Koble-Corrigan). The notably elevated R2 value of 0.99 and a lower ARE % of 14.61 strongly support the assertion that the pseudo-second-order model compromises a superior depiction of the NH3-N reduction process. Furthermore, an effective central composite design (CCD) of response surface methodology (RSM) was employed, and the lower RMSE value, precisely 0.45, demonstrated minimal disparity between the experimentally determined NH3-N removal percentages and those predicted by the model. The subsequent utilization of the desirability function allowed us to attain actual variable experimental conditions.


Assuntos
Carvão Vegetal , Nitrogênio , Titânio , Poluentes Químicos da Água , Titânio/química , Nitrogênio/química , Poluentes Químicos da Água/química , Poluentes Químicos da Água/análise , Carvão Vegetal/química , Amônia/química , Adsorção , Modelos Químicos , Eliminação de Resíduos Líquidos/métodos , Nanocompostos/química
5.
Biosens Bioelectron ; 255: 116254, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38569252

RESUMO

Nitrogen fixation is a key process that sustains life on Earth. Nitrogenase is the sole enzyme capable of fixing nitrogen under ambient conditions. Extensive research efforts have been dedicated to elucidating the enzyme mechanism and its artificial activation through high applied voltage, photochemistry, or strong reducing agents. Harnessing light irradiation to minimize the required external bias can lower the process's high energy investment. Herein, we present the development of photo-bioelectrochemical cells (PBECs) utilizing BiVO4/CoP or CdS/NiO photoanodes for nitrogenase activation toward N2 fixation. The constructed PBEC based on BiVO4/CoP photoanode requires minimal external bias (200 mV) and suppresses O2 generation that allows efficient activation of the nitrogenase enzyme, using glucose as an electron donor. In a second developed PBEC configuration, CdS/NiO photoanode was used, enabling bias-free activation of the nitrogenase-based cathode to produce 100 µM of ammonia at a faradaic efficiency (FE) of 12%. The ammonia production was determined by a commonly used fluorescence probe and further validated using 1H-NMR spectroscopy. The presented PBECs lay the foundation for biotic-abiotic systems to directly activate enzymes toward value-added chemicals by light-driven reactions.


Assuntos
Técnicas Biossensoriais , Nitrogenase , Nitrogenase/química , Nitrogenase/metabolismo , Amônia/química , Fixação de Nitrogênio , Nitrogênio/química
6.
PLoS One ; 19(4): e0299518, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38603769

RESUMO

Wastewater irrigation is a common practice for agricultural systems in arid and semiarid zones, which can help to overcome water scarcity and contribute with nutrient inputs. Ammonia-oxidizing bacteria (AOB) and archaea (AOA) are key in the transformation of NH4+-N in soil and can be affected by variations in soil pH, EC, N and C content, or accumulation of pollutants, derived from wastewater irrigation. The objective of this study was to determine the changes in the ammonia oxidizing communities in agricultural soils irrigated with wastewater for different periods of time (25, 50, and 100 years), and in rainfed soils (never irrigated). The amoA gene encoding for the catalytic subunit of the ammonia monooxygenase was used as molecular reporter; it was quantified by qPCR and sequenced by high throughput sequencing, and changes in the community composition were associated with the soil physicochemical characteristics. Soils irrigated with wastewater showed up to five times more the abundance of ammonia oxidizers (based on 16S rRNA gene relative abundance and amoA gene copies) than those under rainfed agriculture. While the amoA-AOA: amoA-AOB ratio decreased from 9.8 in rainfed soils to 1.6 in soils irrigated for 100 years, indicating a favoring environment for AOB rather than AOA. Further, the community structure of both AOA and AOB changed during wastewater irrigation compared to rainfed soils, mainly due to the abundance variation of certain phylotypes. Finally, the significant correlation between soil pH and the ammonia oxidizing community structure was confirmed, mainly for AOB; being the main environmental driver of the ammonia oxidizer community. Also, a calculated toxicity index based on metals concentrations showed a correlation with AOB communities, while the content of carbon and nitrogen was more associated with AOA communities. The results indicate that wastewater irrigation influence ammonia oxidizers communities, manly by the changes in the physicochemical environment.


Assuntos
Amônia , Solo , Solo/química , Amônia/química , Águas Residuárias , RNA Ribossômico 16S , Archaea/genética , Oxirredução , Microbiologia do Solo , Filogenia , Nitrificação
7.
Chemosphere ; 357: 142049, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38631499

RESUMO

In the face of increasing nitrogen demand for crop cultivation driven by population growth, this study presents a sustainable solution to address both the heightened demand and the energy-intensive process of nitrogen removal from wastewater. Our approach involves the removal of nitrogen from wastewater and its subsequent return to the soil as a fertilizer. Using biochar derived from Aesculus turbinata fruit shells (ATFS), a by-product of post-medical use, we investigated the effect of pyrolysis temperature on the NH4-N adsorption capacity of ATFS biochar (ATFS-BC). Notably, the ATFS-BC pyrolyzed at 300 °C (ATFS-BC300) exhibited the highest NH4-N adsorption capacity of 15.61 mg/g. The superior performance of ATFS-BC300 was attributed to its higher number of oxygen functional groups and more negatively charged surface, which contributed to the enhanced NH4-N adsorption. The removal of NH4-N by ATFS-BC300 involved both physical diffusion and chemisorption, with NH4-N forming a robust multilayer adsorption on the biochar. Alkaline conditions favored NH4-N adsorption by ATFS-BC300; however, the presence of trivalent and divalent ions hindered this process. Rice plants were cultivated to assess the potential of NH4-N adsorbed ATFS-BC300 (NH4-ATFS-BC300) as a nitrogen fertilizer. Remarkably, medium doses of NH4-ATFS-BC300 (594.5 kg/ha) exhibited key agronomic traits similar to those of the commercial nitrogen fertilizer in rice seedlings. Furthermore, high doses of NH4-ATFS-BC300 demonstrated superior agronomic traits compared to the commercial fertilizer. This study establishes the viability of utilizing ATFS-BC300 as a dual-purpose solution for wastewater treatment and nitrogen fertilizer supply, presenting a promising avenue for addressing environmental challenges.


Assuntos
Amônia , Carvão Vegetal , Estudos de Viabilidade , Fertilizantes , Nitrogênio , Águas Residuárias , Carvão Vegetal/química , Águas Residuárias/química , Amônia/química , Adsorção , Frutas/química , Poluentes Químicos da Água/análise , Oryza/crescimento & desenvolvimento , Eliminação de Resíduos Líquidos/métodos
8.
Int J Biol Macromol ; 268(Pt 1): 131617, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38631583

RESUMO

Hydrogels are a promising option for detecting food spoilage in humid conditions, but current indicators are prone to mechanical flaws, posing a concern for packaging systems that require strong mechanical properties. Herein, a double network hydrogel was prepared by polymerizing methacrylamide in a chitosan system with aluminum chloride and glycerol. The resulting hydrogel demonstrated high stretchability (strain >1500 %), notch insensitivity, excellent fatigue resistance, and exceptional anti-freezing capabilities even at -21 °C. When incorporating bromothymol blue (BB) or methyl red (MR), or mixtures of these dyes into the hydrogels as indicators, they exhibited sensitive colorimetric responses to pH and NH3 levels at different temperatures. Hydrogels immobilizing BB to MR ratios of 1:1 and 1:2 displayed clearer and more sensitive color responses when packed into chicken breast, with a sensitivity level of 1.5 ppm of total volatile basic nitrogen (TVB-N). This color response correlated positively with the accumulation of TVB-N on the packaging during storage at both 25 °C and 4 °C, providing sensitive indications of chicken breast deterioration. Overall, the developed hydrogels and indicators demonstrate enhanced performance characteristics, including excellent mechanical strength and highly NH3-sensitive color responses, making significant contributions to the food spoilage detection and intelligent packaging systems field.


Assuntos
Acrilamidas , Amônia , Galinhas , Quitosana , Hidrogéis , Hidrogéis/química , Animais , Amônia/química , Quitosana/química , Acrilamidas/química , Embalagem de Alimentos/métodos , Congelamento
9.
Int J Biol Macromol ; 268(Pt 1): 131750, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38657923

RESUMO

Applications for cotton fabrics with multifunctional qualities, such as flame retardancy, hydrophobicity, and anti-ultraviolet properties, are increasingly common and growing daily. The primary objective of this study is to investigate the preparation of flame retardant, hydrophobic, and ultraviolet (UV) protection cotton fabrics through the utilization of Poly-dimethylsiloxane-co-diphenylsiloxane, dihydroxy terminated (HTDMS) and ammonia phytate (AP). The flame retardancy, thermal stability, mechanical properties, anti-UV properties, air permeability and the hydrophobicity properties of coated cotton fabrics were evaluated. The results indicated that the HTDMS/AP coating was successfully deposited on the surface of cotton fabrics. The damaged length of Cotton/HTDMS/AP was 4.7 cm, and the limiting oxygen index reached 31.5 %. The thermogravimetric analysis revealed that the char residues in the high-temperature range were increased. Furthermore, cone calorimetry results indicated that after the HTDMS/AP coating, the peak heat release rate, total heat release, and total smoke production values decreased by 88.7 %, 51.2 %, and 98.4 %, respectively. Moreover, the deposition of HTDMS/AP provided cotton fabrics with hydrophobicity with a water contact angle of over 130°, while Cotton/HTDMS/AP maintained their air permeability, and enhanced the breaking force compared with those of Cotton/AP. Such desirable qualities make HTDMS/AP a meaningful coating for producing multifunctional cotton fabrics.


Assuntos
Fibra de Algodão , Dimetilpolisiloxanos , Retardadores de Chama , Interações Hidrofóbicas e Hidrofílicas , Dimetilpolisiloxanos/química , Ácido Fítico/química , Amônia/química , Têxteis , Permeabilidade , Resistência à Tração
10.
Int J Mol Sci ; 25(8)2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38673948

RESUMO

A series of bench-stable Co(II) complexes containing hydrazone Schiff base ligands were evaluated in terms of their activity and selectivity in carbon-carbon multiple bond transfer hydrogenation. These cobalt complexes, especially a Co(II) precatalyst bearing pyridine-2-yl-N(Me)N=C-(1-methyl)imidazole-2-yl ligand, activated by LiHBEt3, were successfully used in the transfer hydrogenation of substituted styrenes and phenylacetylenes with ammonia borane as a hydrogen source. Key advantages of the reported catalytic system include mild reaction conditions, high selectivity and tolerance to functional groups of substrates.


Assuntos
Boranos , Cobalto , Bases de Schiff , Hidrogenação , Cobalto/química , Bases de Schiff/química , Catálise , Boranos/química , Complexos de Coordenação/química , Alcinos/química , Amônia/química , Estrutura Molecular
11.
Environ Sci Pollut Res Int ; 31(20): 28997-29016, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38561540

RESUMO

The cement industry is one of the main sources of NOx emissions, and automated denitration systems enable precise control of NOx emission concentration. With non-linearity, time delay and strong coupling data in cement production process, making it difficult to maintain stable control of the denitration system. However, excessive pursuit of denitration efficiency is often prone to large ammonia escape, causing environmental pollution. A multi-objective prediction model combining time series and a bi-directional long short-term memory network (MT-BiLSTM) is proposed to solve the data problem of the denitration system and achieve simultaneous prediction of NOx emission concentration and ammonia escape value. Based on this model, a model predictive control framework is proposed and a control strategy of denitration system with multi-index model predictive control (MI-MPC) is built based on neural networks. In addition, the differential evolution (DE) algorithm is used for rolling optimization to find the optimal solution and to obtain the best control variable parameters. The control method proposed has significant advantages over the traditional PID (proportional integral derivative) controller, with a 3.84% reduction in overshoot and a 3.04% reduction in regulation time. Experiments prove that the predictive control framework proposed in this paper has better stability and higher accuracy, with practical research significance.


Assuntos
Amônia , Óxidos de Nitrogênio , Amônia/química , Materiais de Construção , Modelos Teóricos , Poluição do Ar/prevenção & controle , Algoritmos , Poluentes Atmosféricos
12.
Chemosphere ; 356: 141916, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38583536

RESUMO

This study presents an assessment of inorganic and organic modification of biochar on physicochemical properties, dissolved organic carbon (DOC) release, sorption efficiency towards enrofloxacin (E) and silver nanoparticles (Ag-NPs), as well as an evaluation of addition of prepared materials on hydro-physical properties and adsorption capacity of montmorillonite (M). The biochar was derived from wheat straw at 650 °C. An inorganic modification was performed using ammonia hydroxide, whereas an organic modification, using citric acid. The ammonia hydroxide and citric acid changed the biochar nature and surface chemistry by introducing amino and ester groups. The lowest DOC release was from ammonia-biochar (BCN) and the highest, from citric acid-biochar (BCC). The adsorption data were better described by pseudo-II order equation and Marczewski-Jaroniec isotherm. Results showed that BCN exhibited the highest efficiency in adsorption of E and Ag-NPs. It also improved the adsorptive abilities and saturated hydraulic conductivity of M. This provides the chemically modified biochars have an excellent potential to improve pollution removal from aqueous media and hydro-physical/sorption properties of soil sorption complex. They can be used with advantageous in environmental applications.


Assuntos
Carvão Vegetal , Ácido Cítrico , Nanopartículas Metálicas , Triticum , Triticum/química , Carvão Vegetal/química , Ácido Cítrico/química , Adsorção , Nanopartículas Metálicas/química , Bentonita/química , Prata/química , Enrofloxacina/química , Hidróxidos/química , Amônia/química
13.
Int J Biol Macromol ; 267(Pt 2): 131649, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38636751

RESUMO

The colorless ammonia gas has been a significant intermediate in the industrial sector. However, prolonged exposure to ammonia causes harmful effects to organs or even death. Herein, an environmentally friendly solid-state ammonia sensor was developed utilizing colorimetric polycaprolactone-co-polylactic acid nanofibrous membrane. Pomegranate (Punica granatum L.) peel contains anthocyanin (ACN) as a naturally occurring spectroscopic probe. A mordant (potassium aluminum sulfate) is used to immobilize the anthocyanin direct dyestuff inside nanofibers, generating mordant/anthocyanin (M/ACN) coordinated complex nanoparticles. When exposed to ammonia, the color change of anthocyanin-encapsulated polycaprolactone-co-polylactic acid nanofibrous membrane from purple to transparent was examined by absorbance spectra and CIE Lab color parameters. With a quick colorimetric shift, the polycaprolactone-co-polylactic acid fabric exhibits a detection limit of 5-150 mg/L. The absorbance spectra showed a hypsochromic shift when exposed to ammonia, displaying an absorption shift from 559 nm to 391 nm with an isosbestic point of 448 nm. Scanning electron microscopy (SEM) images revealed that the polycaprolactone-co-polylactic acid nanofibers had a diameter of 75-125 nm, whereas transmission electron microscopy (TEM) images revealed that M/ACN nanoparticles exhibited diameters of 10-20 nm.


Assuntos
Amônia , Antocianinas , Nanofibras , Poliésteres , Nanofibras/química , Poliésteres/química , Antocianinas/química , Amônia/química , Amônia/análise , Gases/química , Colorimetria
14.
Environ Sci Technol ; 58(17): 7653-7661, 2024 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-38635861

RESUMO

The removal and conversion of nitrate (NO3-) from wastewater has become an important environmental and health topic. The NO3- can be reduced to nontoxic nitrogen (N2) for environmental remediation or ammonia (NH3) for recovery, in which the tailoring of the selectivity is greatly challenging. Here, by construction of the CuOx@TiO2 photocatalyst, the NO3- conversion efficiency is enhanced to ∼100%. Moreover, the precise regulation of selectivity to NH3 (∼100%) or N2 (92.67%) is accomplished by the synergy of cooperative redox reactions. It is identified that the selectivity of the NO3- photoreduction is determined by the combination of different oxidative reactions. The key roles of intermediates and reactive radicals are revealed by comprehensive in situ characterizations, providing direct evidence for the regulated selectivity of the NO3- photoreduction. Different active radicals are produced by the interaction of oxidative reactants and light-generated holes. Specifically, the introduction of CH3CHO as the oxidative reactant results in the generation of formate radicals, which drives selective NO3- reduction into N2 for its remediation. The alkyl radicals, contributed to by the (CH2OH)2 oxidation, facilitate the deep reduction of NO3- to NH3 for its upcycling. This work provides a technological basis for radical-directed NO3- reduction for its purification and resource recovery.


Assuntos
Amônia , Nitratos , Oxirredução , Amônia/química , Catálise , Águas Residuárias/química
15.
J Environ Sci (China) ; 143: 12-22, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-38644010

RESUMO

Selective catalytic NH3-to-N2 oxidation (NH3-SCO) is highly promising for abating NH3 emissions slipped from stationary flue gas after-treatment devices. Its practical application, however, is limited by the non-availability of low-cost catalysts with high activity and N2 selectivity. Here, using defect-rich nitrogen-doped carbon nanotubes (NCNT-AW) as the support, we developed a highly active and durable copper-based NH3-SCO catalyst with a high abundance of cuprous (Cu+) sites. The obtained Cu/NCNT-AW catalyst demonstrated outstanding activity with a T50 (i.e. the temperature to reach 50% NH3 conversion) of 174°C in the NH3-SCO reaction, which outperformed not only the Cu catalyst supported on N-free O-functionalized CNTs (OCNTs) or NCNT with less surface defects, but also those most active Cu catalysts in open literature. Reaction kinetics measurements and temperature-programmed surface reactions using NH3 as a probe molecule revealed that the NH3-SCO reaction on Cu/NCNT-AW follows an internal selective catalytic reaction (i-SCR) route involving nitric oxide (NO) as a key intermediate. According to mechanistic investigations by X-ray photoelectron spectroscopy, Raman spectroscopy, and X-ray absorption spectroscopy, the superior NH3-SCO performance of Cu/NCNT-AW originated from a synergy of surface defects and N-dopants. Specifically, surface defects promoted the anchoring of CuO nanoparticles on N-containing sites and, thereby, enabled efficient electron transfer from N to CuO, increasing significantly the fraction of SCR-active Cu+ sites in the catalyst. This study puts forward a new idea for manipulating and utilizing the interplay of defects and N-dopants on carbon surfaces to fabricate Cu+-rich Cu catalysts for efficient abatement of slip NH3 emissions via selective oxidation.


Assuntos
Amônia , Cobre , Oxirredução , Cobre/química , Amônia/química , Catálise , Nanotubos de Carbono/química , Poluentes Atmosféricos/química , Temperatura , Modelos Químicos
16.
Environ Sci Technol ; 58(16): 7228-7236, 2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38551367

RESUMO

The development of electrocatalysts that can efficiently reduce nitrate (NO3-) to ammonia (NH3) has garnered increasing attention due to their potential to reduce carbon emissions and promote environmental protection. Intensive efforts have focused on catalyst development, but a thorough understanding of the effect of the microenvironment around the reactive sites of the catalyst is also crucial to maximize the performance of the electrocatalysts. This study explored an electrocatalytic system that utilized quaternary ammonium surfactants with a range of alkyl chain lengths to modify an electrode made of carbon nanotubes (CNT), with the goal of regulating interfacial wettability toward NO3- reduction. Trimethyltetradecylammonium bromide with a moderate alkyl chain length created a very hydrophobic interface, which led to a high selectivity in the production of NH3 (∼87%). Detailed mechanistic investigations that used operando Fourier-transform infrared (FTIR) spectroscopy and online differential electrochemical mass spectrometry (DEMS) revealed that the construction of a hydrophobic modified CNT played a synergistic role in suppressing a side reaction involving the generation of hydrogen, which would compete with the reduction of NO3-. This electrocatalytic system led to a favorable process for the reduction of NO3- to NH3 through a direct electron transfer pathway. Our findings underscore the significance of controlling the hydrophobic surface of electrocatalysts as an effective means to enhance electrochemical performance in aqueous media.


Assuntos
Amônia , Eletrodos , Nanotubos de Carbono , Nitratos , Molhabilidade , Amônia/química , Nanotubos de Carbono/química , Nitratos/química , Oxirredução , Catálise
17.
Dent Mater ; 40(5): 777-788, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38458917

RESUMO

OBJECTIVE: To evaluate the effects of an ammonia-based and a water-based silver-containing solutions on bonding performance and matrix-metalloproteinases (MMPs) activity of a universal adhesive to dentin after 1 year of artificial aging. METHODS: Mid-coronal dentin surfaces of 60 sound human molars were exposed and the following groups were formed according to the surface pre-treatment and etching mode of the universal adhesive (Zipbond Universal, SDI) (n = 10): G1) Zipbond in the self-etch mode (ZSE); G2) Riva Star (SDI) applied before ZSE; G3) Riva Star Aqua (SDI) applied before ZSE; G4) Zipbond in the etch-and-rinse mode (ZER); G5) Riva Star applied before ZER; G6) Riva Star Aqua applied before ZER. The specimens were sectioned and subjected to microtensile bond strength (µTBS) test at baseline (T0) and after 12 months (T12) of artificial storage. Scanning electron microscope (SEM) and energy dispersive spectroscopy analysis (EDS) were also conducted. Three additional molars per group were processed for the in situ zymography analysis at T0 and T12. Data were statistically analyzed (p < 0.05). RESULTS: Dentin pre-treatments and aging decreased bonding values, regardless of the etching mode (p < 0.05). No differences in µTBS were observed between the two silver-containing solutions, both at T0 and T12. Riva Star Aqua and etching significantly increased the MMPs activity, independent of the storage period (p < 0.05). SIGNIFICANCE: Dentin surface pre-treatment with silver-containing solutions negatively affects the bonding performances of resin composite restorations placed with a universal adhesive. However, the ammonia-based product Riva Star might show better stability in the long term, due to lower activation of MMPs.


Assuntos
Amônia , Colagem Dentária , Adesivos Dentinários , Teste de Materiais , Microscopia Eletrônica de Varredura , Prata , Propriedades de Superfície , Resistência à Tração , Água , Humanos , Água/química , Adesivos Dentinários/química , Prata/química , Amônia/química , Dentina/química , Técnicas In Vitro , Metaloproteinases da Matriz/metabolismo , Metaloproteinases da Matriz/química , Cimentos de Resina/química , Dente Molar , Condicionamento Ácido do Dente , Espectrometria por Raios X , Análise do Estresse Dentário
18.
Biotechnol Adv ; 72: 108341, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38499256

RESUMO

Lignocellulosic biomass holds a crucial position in the prospective bio-based economy, serving as a sustainable and renewable source for a variety of bio-based products. These products play a vital role in displacing fossil fuels and contributing to environmental well-being. However, the inherent recalcitrance of biomass poses a significant obstacle to the efficient access of sugar polymers. Consequently, the bioconversion of lignocellulosic biomass into fermentable sugars remains a prominent challenge in biorefinery processes to produce biofuels and biochemicals. In addressing these challenges, extensive efforts have been dedicated to mitigating biomass recalcitrance through diverse pretreatment methods. One noteworthy process is Ammonia Fiber Expansion (AFEX) pretreatment, characterized by its dry-to-dry nature and minimal water usage. The volatile ammonia, acting as a catalyst in the process, is recyclable. AFEX contributes to cleaning biomass ester linkages and facilitating the opening of cell wall structures, enhancing enzyme accessibility and leading to a fivefold increase in sugar conversion compared to untreated biomass. Over the last decade, AFEX has demonstrated substantial success in augmenting the efficiency of biomass conversion processes. This success has unlocked the potential for sustainable and economically viable biorefineries. This paper offers a comprehensive review of studies focusing on the utilization of AFEX-pretreated biomass in the production of second-generation biofuels, ruminant feed, and additional value-added bioproducts like enzymes, lipids, proteins, and mushrooms. It delves into the details of the AFEX pretreatment process at both laboratory and pilot scales, elucidates the mechanism of action, and underscores the role of AFEX in the biorefinery for developing biofuels and bioproducts, and nutritious ruminant animal feed production. While highlighting the strides made, the paper also addresses current challenges in the commercialization of AFEX pretreatment within biorefineries. Furthermore, it outlines critical considerations that must be addressed to overcome these challenges, ensuring the continued progress and widespread adoption of AFEX in advancing sustainable and economically viable bio-based industries.


Assuntos
Amônia , Biocombustíveis , Amônia/química , Amônia/farmacologia , Biomassa , Estudos Prospectivos , Lignina/metabolismo , Açúcares
19.
J Environ Manage ; 355: 120504, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38447513

RESUMO

Ammonia-oxidation process directly contribute to soil nitrous oxide (N2O) emissions in agricultural soils. However, taxonomy of the key nitrifiers (within ammonia oxidising bacteria (AOB), archaea (AOA) and complete ammonia oxidisers (comammox Nitrospira)) responsible for substantial N2O emissions in agricultural soils is unknown, as is their regulation by soil biotic and abiotic factors. In this study, cumulative N2O emissions, nitrification rates, abundance and community structure of nitrifiers were investigated in 16 agricultural soils from major crop production regions of China using microcosm experiments with amended nitrogen (N) supplemented or not with a nitrification inhibitor (nitrapyrin). Key nitrifier groups involved in N2O emissions were identified by comparative analyses of the different treatments, combining sequencing and random forest analyses. Soil cumulative N2O emissions significantly increased with soil pH in all agricultural soils. However, they decreased with soil organic carbon (SOC) in alkaline soils. Nitrapyrin significantly inhibited soil cumulative N2O emissions and AOB growth, with a significant inhibition of the AOB Nitrosospira cluster 3a.2 (D11) abundance. One Nitrosospira multiformis-like OTU phylotype (OTU34), which was classified within the AOB Nitrosospira cluster 3a.2 (D11), had the greatest importance on cumulative N2O emissions and its growth significantly depended on soil pH and SOC contents, with higher growth at high pH and low SOC conditions. Collectively, our results demonstrate that alkaline soils with low SOC contents have high N2O emissions, which were mainly driven by AOB Nitrosospira cluster 3a.2 (D11). Nitrapyrin can efficiently reduce nitrification-related N2O emissions by inhibiting the activity of AOB Nitrosospira cluster 3a.2 (D11). This study advances our understanding of key nitrifiers responsible for high N2O emissions in agricultural soils and their controlling factors, and provides vital knowledge for N2O emission mitigation in agricultural ecosystems.


Assuntos
Ecossistema , Solo , Solo/química , Amônia/química , Carbono , Oxirredução , Archaea , Nitrificação , Microbiologia do Solo
20.
Environ Sci Pollut Res Int ; 31(11): 17372-17386, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38340300

RESUMO

Multi-pollutant removal (MPR) of NO and VOCs simultaneously is efficient of flue gas treatment in coal-fired power plants. But reducing the competition for active sites between NH3, NO, C6H6, and C7H8 remains challenging. Herein, Cr, Mn, and Fe were respectively doped to MoWTi catalyst via wet impregnation. The Fe3+ + Mo5+ ↔ Fe2+ + Mo6+ redox cycle led to an increased proportion of low valence ions (Mo5+ and W5+) and facilitated the creation of active oxygen vacancies with several active sites. It also possessed plentiful mild to strong acid sites with ideal ratio. These factors enhanced catalytic activity of Fe-MoWTi. Remarkable MPR efficiencies of NO, C6H6, and C7H8 were achieved under industrial SCR condition, characterized by low oxygen but high SO2 levels at 340 °C, with removal rates reaching 89.85%, 97.57%, and 86.30% respectively. Theory calculations further revealed that Fe-MoWTi favor NH3 and O2 adsorptions. NO elimination was found to follow both Eley-Rideal (E-R) and Langmuir-Hinshelwood (L-H) processes, supported by in situ DRIFTS analysis. The reactions involving NO/NO2/nitrite/nitrate occurred with NH3(ads)/ NH4+(ads)/NH2 (ads). C6H6 and C7H8 underwent gradual oxidation, formatting alcohols, aldehydes, acids, and maleic acids, before eventually being mineralized to gaseous CO2 and H2O. Findings hold significant potential for application, providing guidance for the development of catalysts with improved resistance against SO2 poisoning and enhanced MPR capabilities.


Assuntos
Poluentes Ambientais , Domínio Catalítico , Amônia/química , Oxirredução , Oxigênio , Catálise
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