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1.
J Am Chem Soc ; 146(10): 6466-6470, 2024 Mar 13.
Artículo en Inglés | MEDLINE | ID: mdl-38428040

RESUMEN

N-heterocyclic carbenes (NHCs) have been extensively studied to modulate the reactivity of molecular catalysts, colloids, and their supported analogues, being isolated sites, clusters, or nanoparticles. While the interaction of NHCs on metal surfaces has been discussed in great detail, showing specific coordination chemistry depending on the type of NHC ligands, much less is known when the metal is dispersed on oxide supports, as in heterogeneous catalysts. Herein, we study the interaction of NHC ligands with Au surface sites dispersed on silica, a nonreducible oxide support. We identify the easy formation of bis-NHC ligated Au(I) surface sites parallel to what is found on metallic Au surfaces. These species display a specific 13C NMR spectroscopic signature that clearly distinguishes them from the mono-NHC Au(I) surface sites or supported imidazoliums. We find that bis-ligated surface species are not unique to supported Au(I) species and are found for the corresponding Ag(I) and Cu(I) species, as well as for the isolobal surface silanols. Furthermore, the interaction of NHC ligand with silica-supported Au nanoparticles also yields bis-NHC ligated Au(I) surface sites, indicating that metal atoms can also be easily extracted from nanoparticles, further illustrating the dynamics of these systems and the overall favorable formation of such bis-ligated species across a range of systems, besides what has been found on crystalline metal facets.

2.
J Am Chem Soc ; 145(23): 12928-12934, 2023 Jun 14.
Artículo en Inglés | MEDLINE | ID: mdl-37267262

RESUMEN

Selective oxidation of methane to methanol by dioxygen (O2) is an appealing route for upgrading abundant methane resource and represents one of the most challenging reactions in chemistry due to the overwhelmingly higher reactivity of the product (methanol) versus the reactant (methane). Here, we report that gold nanoparticles dispersed on mordenite efficiently catalyze the selective oxidation of methane to methanol by molecular oxygen in aqueous medium in the presence of carbon monoxide. The methanol productivity reaches 1300 µmol gcat-1 h-1 or 280 mmol gAu-1 h-1 with 75% selectivity at 150 °C, outperforming most catalysts reported under comparable conditions. Both hydroxyl radicals and hydroperoxide species participate in the activation and conversion of methane, while it is shown that the lower affinity of methanol on gold mainly accounts for higher methanol selectivity.

3.
Anal Chem ; 95(2): 792-801, 2023 01 17.
Artículo en Inglés | MEDLINE | ID: mdl-36520837

RESUMEN

Ligand exchange is fundamentally related to the surface chemistry of nanoparticles in solution and is also an essential procedure for their synthesis and solution processing. The solution of ligand-bearing nanoparticles can be regarded as a dynamic equilibrium of bound and free ligands depending on the concentration and temperature. The direct experimental calibration of the ligand exchange dynamics relies on the in situ and real-time quantification of bound and free ligands. However, existing analytical strategies are often with limited applicability considering the requirement of special functional groups or the indirect detection of photoluminescence or reaction heat. In this work, we explore diffusion-based methods of solution-state nuclear magnetic resonance (NMR) as a general strategy to probe ligand exchange. Using comprehensive numerical simulations, we show that diffusion NMR with designable time sequences can effectively distinguish bound and free ligands and measure the exchange rate constants from 0.5 to 200 s-1 under typical instrumental settings. These methods are demonstrated experimentally on colloidal CdSe nanocrystal systems with carboxylate or amine ligands whose exchange rates were previously undetectable. The kinetic rate constants, activation energies, and thermodynamic parameters of ligand exchange have been obtained under variable temperature conditions. We expect the diffusion NMR strategies to be generally applicable for calibrating the exchange of organic ligands on various nanoparticle systems.


Asunto(s)
Nanopartículas , Ligandos , Nanopartículas/química , Espectroscopía de Resonancia Magnética , Termodinámica , Temperatura
4.
Angew Chem Int Ed Engl ; 62(50): e202312713, 2023 Dec 11.
Artículo en Inglés | MEDLINE | ID: mdl-37869935

RESUMEN

Converting colloidal nanocrystals (NCs) into devices for various applications is facilitated by designing and controlling their surface properties. One key strategy for tailoring surface properties is thus to choose tailored surface ligands. In that context, amines have been universally used, with the goal to improve NCs synthesis, processing and performances. However, understanding the nature of surface sites in amine-capped NCs remains challenging, due to the complex surface compositions as well as surface ligands dynamic. Here, we investigate both surface sites and amine ligation in CdSe NCs by combining advanced NMR spectroscopy and computational modelling. Notably, dynamic nuclear polarization (DNP) enhanced 113 Cd and 77 Se 1D NMR helps to identify both bulk and surface sites of NCs, while 113 Cd 2D NMR spectroscopy enables to resolve amines terminated sites on both Se-rich and nonpolar surfaces. In addition to directly bonding to surface sites, amines are shown to also interact through hydrogen-bonding with absorbed water as revealed by 15 N NMR, augmented with computations. The characterization methodology developed for this work provides unique molecular-level insight into the surface sites of a range of amine-capped CdSe NCs, and paves the way to identify structure-function relationships and rational approaches towards colloidal NCs with tailored properties.

5.
Nanotechnology ; 33(49)2022 Sep 19.
Artículo en Inglés | MEDLINE | ID: mdl-36044817

RESUMEN

Carbon impurity as point defects makes key impact on the leakage in GaN-on-Si structures. GaN-based epitaxial layers with different point defects by changing carbon-doped concentration were used to investigate the point defects behavior. It was found that leakage mechanisms correspond with space-charge-limited current models at low voltages, and after 1st kink, electron injection from silicon to GaN and PF conduction play a key role in the leakage of both point defects case with low carbon and high carbon doped. In addition, high carbon in GaN-on-Si epitaxial layers obtained lower leakage and larger breakdown voltage. The slope of logJ-Vhas two kinks and effective energy barrierEahas two peaks, 0.4247 eV at about 300 V and 0.3485 eV at about 900 V, respectively, which is related to accepted states and donor states related with carbon impurity. While the slope of logJ-Vhas one kink and effective energy barrierEahas one peak, 0.4794 eV at about 400 V of low carbon in GaN-on-Si epitaxial layers, indicating only field-induced accepted ionized makes impact on leakage. The comparative results of more donor trap density in high carbon indicate point defects related with carbon impurity play a key role in the kinks of logJ-Vslope.

6.
J Environ Sci (China) ; 112: 376-387, 2022 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-34955220

RESUMEN

Nanoparticles (NPs) are widely used for their special physical properties and released into the natural environment. When two types of NPs exist in the same environment, the presence of one type of NP may affect the properties of the other type of NP. This study investigated the toxic effects of multi-walled carbon nanotubes (MWCNTs) and copper oxide nanoparticles (CuO NPs) on Tetradesmus obliquus. Both NPs had toxic effects on algae, and the toxic effects of MWCNTs were significantly stronger than CuO NPs which the 96-hr median effective concentration to algae were 33.8 and 169.2 mg/L, respectively. Oxidative stress and cell membrane damage were the main reasons for the toxicity of NPs to algae, and they were concentration-dependent, and the existence of CuO NPs in some groups reduced cell membrane damage caused by MWCNTs which may because that CuO NPs formed heteroaggregation with MWCNTs, reducing the contact of nanoparticles with cell membranes, then reducing physical damage. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) results indicated cell damage, the heteroaggregation of MWCNTs-CuO NPs and obvious nanoparticles internalization. In some groups, the presence of CuO NPs significantly reduced reactive oxygen species (ROS) level induced by MWCNTs. However, for the highest concentration group, the ROS level was much higher than that of the two NPs alone treatment groups, which might be related to the high concentration of MWCNTs promoting the internalization of CuO NPs. MWCNTs and CuO NPs affected and interacted with each other, causing more complex toxic effects on aquatic organisms.


Asunto(s)
Chlorophyta/efectos de los fármacos , Cobre , Nanopartículas del Metal , Nanotubos de Carbono , Cobre/toxicidad , Agua Dulce , Nanopartículas del Metal/toxicidad , Nanotubos de Carbono/toxicidad , Óxidos , Especies Reactivas de Oxígeno , Contaminantes Químicos del Agua/toxicidad
7.
Nano Lett ; 20(2): 829-840, 2020 02 12.
Artículo en Inglés | MEDLINE | ID: mdl-31916446

RESUMEN

Breast cancer metastases to bone poses a significant challenge for the administration of treatment strategies. The bone microenvironment, metastatic tumor cells, osteoclasts, and tumor-associated macrophages (TAMs) all play crucial and synergistic roles in creating a favorable environment for the proliferation, progression, and survival of the metastatic tumor, which in turn induces osteoclast-mediated bone destruction. In this study, we functionalized immunostimulatory cytosine-phosphate-guanosine (CpG)-loaded metal-organic framework (MOF) nanoparticles with bone targeting capabilities by surface modification with FDA approved antiresorptive bisphosphonate, zoledronic acid (ZOL). The functionalized bone targeting immunostimulatory MOF (BT-isMOF) nanoparticles demonstrates strong binding to calcium phosphate in vitro and exhibits specific targeting and accumulation in bone tissues in vivo. In vitro cellular and biochemical analyses demonstrated that the BT-isMOF nanoparticles could potently inhibit osteoclast formation and concomitantly induce macrophages polarization toward the M1 pro-inflammatory phenotype. Finally, using the intratibial murine model of breast cancer bone metastasis, we showed that the administration of BT-isMOF nanoparticles significantly suppressed osteoclast-mediated bone destruction and enhanced polarization of tumor-resident macrophages to M1 phenotype. Together, our data provides promising evidence for the potential therapeutic application of the BT-isMOF nanoparticles in the treatment of breast cancer bone metastases.


Asunto(s)
Neoplasias Óseas/tratamiento farmacológico , Neoplasias de la Mama/tratamiento farmacológico , Estructuras Metalorgánicas/farmacología , Nanopartículas/química , Animales , Conservadores de la Densidad Ósea/química , Conservadores de la Densidad Ósea/farmacología , Neoplasias Óseas/patología , Neoplasias Óseas/secundario , Neoplasias de la Mama/patología , Línea Celular Tumoral , Difosfonatos/química , Difosfonatos/farmacología , Femenino , Humanos , Estructuras Metalorgánicas/química , Ratones , Oligodesoxirribonucleótidos/química , Oligodesoxirribonucleótidos/farmacología , Osteoclastos/efectos de los fármacos , Osteólisis/tratamiento farmacológico , Osteólisis/patología , Macrófagos Asociados a Tumores/efectos de los fármacos , Ácido Zoledrónico/química , Ácido Zoledrónico/farmacología
8.
Angew Chem Int Ed Engl ; 60(14): 7719-7727, 2021 03 29.
Artículo en Inglés | MEDLINE | ID: mdl-33400342

RESUMEN

Understanding of drug-carrier interactions is essential for the design and application of metal-organic framework (MOF)-based drug-delivery systems, and such drug-carrier interactions can be fundamentally different for MOFs with or without defects. Herein, we reveal that the defects in MOFs play a key role in the loading of many pharmaceuticals with phosphate or phosphonate groups. The host-guest interaction is dominated by the Coulombic attraction between phosphate/phosphonate groups and defect sites, and it strongly enhances the loading capacity. For similar molecules without a phosphate/phosphonate group or for MOFs without defects, the loading capacity is greatly reduced. We employed solid-state NMR spectroscopy and molecular simulations to elucidate the drug-carrier interaction mechanisms. Through a synergistic combination of experimental and theoretical analyses, the docking conformations of pharmaceuticals at the defects were revealed.


Asunto(s)
Adenosina Monofosfato/química , Estructuras Metalorgánicas/química , Nanocápsulas/química , Compuestos Organometálicos/química , Ácidos Ftálicos/química , Composición de Medicamentos , Liberación de Fármacos , Conformación Molecular , Simulación del Acoplamiento Molecular , Organofosfonatos/química , Fosfatos/química , Porosidad , Propiedades de Superficie
9.
Nano Lett ; 19(3): 1618-1624, 2019 03 13.
Artículo en Inglés | MEDLINE | ID: mdl-30716273

RESUMEN

Metal-organic frameworks (MOFs) are porous crystalline materials with promising applications in molecular adsorption, separation, and catalysis. It has been discovered recently that structural defects introduced unintentionally or by design could have a significant impact on their properties. However, the exact chemical composition and structural evolution under different conditions at the defects are still under debate. In this study, we performed multidimensional solid-state nuclear magnetic resonance (SSNMR) coupled with computer simulations to elucidate an important scenario of MOF defects, uncovering the dynamic interplay between residual acetate and water. Acetate, as a defect modulator, and water, as a byproduct, are prevalent defect-associated species, which are among the key factors determining the reactivity and stability of defects. We discovered that acetate molecules coordinate to a single metal site monodentately and pair with water at the neighboring position. The acetates are highly flexible, which undergo fast libration as well as a slow kinetic exchange with water through dynamic hydrogen bonds. The dynamic processes under variable temperatures and different hydration levels have been quantitatively analyzed across a broad time scale from microseconds to seconds. The integration of SSNMR and computer simulations allows a precision probe into defective MOF structures with intrinsic dynamics and disorder.

10.
J Am Chem Soc ; 141(39): 15675-15683, 2019 10 02.
Artículo en Inglés | MEDLINE | ID: mdl-31503473

RESUMEN

Aliphatic carboxylates are the most common class of surface ligands to stabilize colloidal nanocrystals. The widely used approach to identify the coordination modes between surface cationic sites and carboxylate ligands is based on the empirical infrared (IR) spectroscopic assignment, which is often ambiguous and thus hampers the practical control of surface structures. In this report, multiple techniques based on nuclear magnetic resonance (NMR) and IR spectra are applied to distinguish the different coordination structures in a series of zinc-blende CdSe nanocrystals with unique facet structures, including nanoplatelets dominated with {100} basal planes, hexahedrons with only three types of low-index facets (i.e., {100}, {110}, and {111}), and spheroidal dots without well-defined facets. Interpretation and assignment of NMR and IR signals were assisted by density functional theory (DFT) calculations. In addition to the identification of facet-sensitive bonding modes, the present methods also allow a nondestructive quantification of mixed ligands.

11.
Angew Chem Int Ed Engl ; 58(49): 17764-17770, 2019 Dec 02.
Artículo en Inglés | MEDLINE | ID: mdl-31591763

RESUMEN

Facet-dependent on-surface reactions are systematically studied on zinc-blende CdSe nanoplatelets with atomically-flat {001} basal facets and small yet non-polar side facets. The on-surface half-reactions between the surface Se sites and Cd carboxylates in the solution are qualitatively equivalent to those on the spheroidal counterparts. Conversely, the on-surface half-reactions between the surface Cd sites and the activated Se precursors in solution show a strong facet-dependence, which includes three distinguishable stages. In the first stage, the Se precursors adsorb onto the small and non-polar side facets of the nanoplatelets. The second stage is initiated by the adsorbed Se precursors at the side-basal plane edges and proceeds from the edges to the center of the basal planes in quasi-zeroth-order kinetics. In the third stage, the nanoplatelets are dismantled, which includes the creation of a hole in the middle and a build-up of thick edges.

12.
Ecotoxicol Environ Saf ; 158: 162-170, 2018 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-29684746

RESUMEN

Sulfate-reducing bacteria (SRB), a group of anaerobic prokaryotes, can use sulfur species as a terminal electron acceptor for the oxidation of organic compounds. They not only have significant ecological functions, but also play an important role in bioremediation of contaminated sites. Although numerous studies on metabolism and applications of SRB have been conducted, they still remain incompletely understood and even controversial. Fully understanding the metabolism of SRB paves the way for allowing the microorganisms to provide more beneficial services in bioremediation. Here we review progress in bioenergetics mechanisms and application of SRB including: (1) electron acceptors and donors for SRB; (2) pathway for sulfate reduction; (3) electron transfer in sulfate reduction; (4) application of SRB for economical and concomitant treatment of heavy metal, organic contaminants and sulfates. Moreover, current knowledge gaps and further research needs are identified.


Asunto(s)
Bacterias Anaerobias/metabolismo , Metabolismo Energético , Sulfatos/metabolismo , Bacterias Reductoras del Azufre/metabolismo , Biodegradación Ambiental , Transporte de Electrón , Hidrocarburos Clorados/análisis , Hidrógeno/metabolismo , Metales Pesados/análisis , Oxidación-Reducción , Aguas Residuales/química , Aguas Residuales/microbiología , Contaminantes del Agua/análisis
13.
J Hazard Mater ; 465: 133098, 2024 Mar 05.
Artículo en Inglés | MEDLINE | ID: mdl-38064949

RESUMEN

In mineral-rich areas, eutrophic lakes are at risk of HMs pollution. However, few papers focused on the repair of HMs in eutrophic environment. Our study analyzed multiple forms of HMs, pore structure and microbial responses in the water-sediment system of eutrophic lake treated with biochar, Effective Microorganisms (EMs) or/and microplastics (MPs). As biochar provided an ideal carrier for EMs, the remediation of biochar-supported EMs (BE) achieved the greatest repairment that improved the bacterial indexes and greatly decreased the most HMs in various forms across the water-sediment system, and it also reduced metal mobility, bioavailability and ecological risk. The addition of aged MPs (MP) stimulated the microbial activity and significantly reduced the HMs levels in different forms due to the adsorption of biofilms/EPS adhered on MPs, but it increased metals mobility and ecological risks. The strong adsorption and high mobility of aged MPs would increase enrichment of HMs and cause serious ecological hazards. The incorporation of BE and MP (MBE) also greatly reduced the HMs in full forms, which was primarily ascribed to the adsorption of superfluous biofilms/EPS, but it distinctly depressed the microbial activity. The single addition of biochar and EMs resulted in the inability of HMs to be adsorbed due to the preferentially adsorption of dissolved nutrients and the absence of effective carrier, respectively. In the remediation cases, the remarkable removal of HMs was principally accomplished by the adsorption of HMs with molecular weight below 100 kDa, especially 3 kDa ∼100 kDa, which had higher specific surfaces and abundant active matters, resulting in higher adsorption onto biofilms/EPS.


Asunto(s)
Carbón Orgánico , Metales Pesados , Microplásticos , Plásticos , Lagos , Metales Pesados/análisis , Agua
14.
Chem Sci ; 15(8): 3028-3032, 2024 Feb 22.
Artículo en Inglés | MEDLINE | ID: mdl-38404381

RESUMEN

Molecular-level understanding of the acid/base properties of heterogeneous catalysts requires the development of selective spectroscopic probes to establish structure-activity relationships. In this work we show that substituting the surface protons in oxide supports by isolobal N-heterocyclic carbene (NHC) Ag cations and measuring their 109Ag nuclear magnetic resonance (NMR) signatures enables to probe the speciation and to evaluate the corresponding Brønsted acidity of the substituted OH surface sites. Specifically, a series of silver N-heterocyclic carbene (NHC) Ag(i) complexes of general formula [(NHC)AgX] are synthesized and characterized, showing that the 109Ag NMR chemical shift of the series correlates with the Brønsted acidity of the conjugate acid of X- (i.e., HX), thus establishing an acidity scale based on 109Ag NMR chemical shift. The methodology is then used to evaluate the Brønsted acidity of the OH sites of representative oxide materials using Dynamic Nuclear Polarization (DNP-)enhanced solid-state NMR spectroscopy.

15.
Sci Total Environ ; 923: 171476, 2024 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-38458471

RESUMEN

DOM (dissolved organic matter) play a crucial role in lakes' geochemical and carbon cycles. Eutrophication evolution would influence nutrient status of waters and investigating the DOM variation helps a better understanding of bioremediation on environmental behavior of DOM in eutrophic lakes. In our study, the contents, compositions and characteristics of systematic DOM&SOM (sediment organic matter) were greatly influenced by seasonal changes. But the effective bioremediations obviously reduced the DOM concentration and thus mitigated the eutrophication outbreak risks in water bodies due to the increased MBC (microbial biomass carbon), microbial activity and metabolism. In early summer, the overall DOM in each treatment were readily low levels and derived from both autochthonous and exogenous origins, dominated by fulvic acid-like. In midsummer, the DOM contents and characteristics in each treatment increased significantly as phytoplankton activity improved, and the majority of DOM were humic acid-like and mainly of biological origin. The greatest differences of enzymes, MBC, microbial metabolism and DOM&SOM removal among different treatments were observed in summer months. In autumn, the systematic DOM&SOM slightly reduced due to the deceased microbial activity, in which the microbial humic acids were main component and derived from endogenous sources. Additionally, the gradually decreased SOM with cultivated time in each treatment was a result of microbiological conversion of SOM into DOM. For various treatments, BE, BE.A, BE.C and BE.E increased the MBC, enzymatic and microbial activities due to the application of biochar-supported EMs. Among these, BE and BE.A, especially BE.A with oxygen supplement, achieved the most desirable effect on reducing systematic DOM&SOM levels and increasing enzymatic and microbial activities. The group of EM also reduced the levels of DOM&SOM as improved degradation of EMs for DOM. However, BC, BE.C and BE.E finally did not achieved the desirable effect on reducing DOM&SOM due to the suppression of microbial activities, respectively, from high dose of biochar, weakening of dominant species and additional introduction of EMs in low liveness.


Asunto(s)
Materia Orgánica Disuelta , Lagos , Lagos/química , Estaciones del Año , Carbón Orgánico , Sustancias Húmicas/análisis
16.
Sci Total Environ ; 956: 177142, 2024 Nov 04.
Artículo en Inglés | MEDLINE | ID: mdl-39486534

RESUMEN

Lots of studies on eutrophication, but there is a lack of comprehensive research on the repair of multiple forms of nitrogen and phosphorus under combined heavy metals (HMs) pollution. This work investigated the various forms of nitrogen and phosphorus in the water-sediment systems of eutrophic lakes with the application of biochar, Effective Microorganisms (EMs) and microplastics, aiming to deliberate the repair behavior of multiple forms of nitrogen/phosphorus and the integrated repairment of these nutrients and HMs in different remediations. For amended-groups, the application of biochar-supported EMs (BE) achieved the most desirable remediation for removing nitrogen, phosphorus and HMs in water and improved their stability in sediment due to the improved microbial activity and the developed biofilm system created by biochar. The addition of aging microplastics (MP) obviously reduced the systematic levels of nitrogen, phosphorus and HMs due to the stimulation of microbial activity and the adsorption of biofilm/EPS, but its high movability also increased the Fe(II) and S(-II) levels and the pollutants' ecological risks in sediment. The co-application of BE and MP (MBE) destroyed the ecosystem and decreased the removal of nitrogen and phosphorus, while greatly removing HMs by the superfluous biofilms/EPS. The application of biochar (BC) preferentially adsorbed and degraded dissolved nitrogen and phosphorus, releasing HMs into water. From these amended-groups, it's also knew that the removal of nitrogen and phosphorus mainly came from the degradation/assimilation of NH3-N, SRP and dissolved matters, particularly those molecular weight below 3 kDa; the higher removal of phosphorus than nitrogen was attributed to the coprecipitation of Fe-S-P hydroxides and the adsorption of particulates; however, the colloidal (3-100 kDa) nitrogen and phosphorus had low accessibility and bioavailability, and it also showed the competitive adsorption with colloidal HMs, causing their relatively low removal in water. This study provides insight into the comprehensive repair of nitrogen, phosphorus and HMs in various forms by biochar-immobilized microbes and the influence of microplastics on nutrients and HMs in eutrophic lakes.

17.
Sci Total Environ ; 916: 170101, 2024 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-38242474

RESUMEN

The presence of residual antibiotics in the environment is a prominent issue. Photodegradation behavior is an important way of antibiotics reduction, which is closely related to dissolved organic matter (DOM) in water. The review provides an overview of the latest advancements in the field. Classification, characterization of DOM, and the dominant mechanisms for antibiotic photodegradation were discussed. Furthermore, it summarized and compared the effects of DOM on different antibiotics photodegradation. Moreover, the review comprehensively considered the factors influencing the photodegradation of antibiotics in the aquatic environment, including the characteristics of light, temperature, dosage of DOM, concentration of antibiotics, solution pH, and the presence of coexisting ions. Finally, potential directions were proposed for the development of predictive models for the photodegradation of antibiotics. Based on the review of existing literature, this paper also considered several pathways for the future study of antibiotic photodegradation. This study allows for a better understanding of the DOM's environmental role and provides important new insights into the photochemical fate of antibiotics in the aquatic environment.


Asunto(s)
Antibacterianos , Contaminantes Químicos del Agua , Materia Orgánica Disuelta , Fotólisis , Contaminantes Químicos del Agua/química , Agua/química
18.
Sci Rep ; 13(1): 14820, 2023 Sep 08.
Artículo en Inglés | MEDLINE | ID: mdl-37684297

RESUMEN

Carbon doping in GaN-on-Silicon (Si) epitaxial layers is an essential way to reduce leakage current and improve breakdown voltage. However, complicated occupy forms caused by carbon lead to hard analysis leakage/breakdown mechanisms of GaN-on-Si epitaxial layers. In this paper, we demonstrate the space charge distribution and intensity in GaN-on-Si epitaxial layers from 0 to 448 V by simulation. Depending on further monitoring of the trapped charge density of CN and CGa in carbon-doped GaN at 0.1 µm, 0.2 µm, 1.8 µm and 1.9 µm from unintentionally doped GaN/carbon-doped GaN interface, we discuss the relationship between space charge and plateau, breakdown at CN concentrations from 6 × 1016 cm-3 to 6 × 1018 cm-3. The results show that CN in different positions of carbon-doped GaN exhibits significantly different capture and release behaviors. By utilizing the capture and release behavior differences of CN at different positions in carbon-doped GaN, the blocking effect of space charge at unintentionally doped GaN/carbon-doped GaN interface on electron conduction was demonstrated. The study would help to understand the behavior of CN and CGa in GaN-on-Si epitaxial layers and more accurate control of CN and CGa concentration at different positions in carbon-doped GaN to improve GaN-on-Si device performance.

19.
ACS Appl Mater Interfaces ; 15(28): 34272-34289, 2023 Jul 19.
Artículo en Inglés | MEDLINE | ID: mdl-37415272

RESUMEN

Dye/salt separation in textile wastewater is of great importance. Membrane filtration technology is an environmentally friendly and effective approach to solve this issue. In this study, a thin-film composite membrane with a tannic acid (TA)-modified carboxylic multiwalled carbon nanotube (MWCNT) interlayer (M-TA) was prepared by interfacial polymerization with amino-functionalized graphene quantum dots (NGQDs) acting as aqueous monomers. The addition of the M-TA interlayer favored the formation of a thinner, more hydrophilic, and smoother selective skin layer for the composite membrane. The pure water permeability of the M-TA-NGQDs membrane was ∼9.32 L m-2 h-1 bar-1, which was higher than that of the NGQDs membrane without the interlayer. Meanwhile, the M-TA-NGQDs membrane presented better methyl orange (MO) rejection (97.79%) than the NGQDs membrane (87.51%). The optimal M-TA-NGQDs membrane exhibited excellent dye rejection (Congo red (CR): 99.61%; brilliant green (BG): 96.04%) and low salt rejection (NaCl < 15%). Noticeably, the M-TA-NGQDs membrane displayed effective selective separation performance (CR and BG > 99%) for dye/NaCl mixed solutions even at a high NaCl concentration of 50,000 mg/L. Furthermore, the M-TA-NGQDs membrane presented high water permeability recovery ratio values (91.02-98.20%). Importantly, the M-TA-NGQDs membrane showed excellent chemical stability (acid/alkali resistance). Generally, the fabricated M-TA-NGQDs membrane exhibited a great prospect for applications in dye wastewater treatment and water recycling, especially for the effective selective separation of dye/salt mixtures for high-salinity textile dyeing wastewater.

20.
J Colloid Interface Sci ; 641: 197-214, 2023 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-36933467

RESUMEN

For better sustainable resource recovery and elevating the separation efficiency of dye/salt mixture, it is essential to develop an appropriate nanofiltration membrane for the treatment of textile dyeing wastewater containing relatively smaller molecule dyes. In this work, a novel composite polyamide-polyester nanofiltration membrane was fabricated by tailoring amino functionalized quantum dots (NGQDs) and ß-cyclodextrin (CD). An in-situ interfacial polymerization occurred between the synthesized NGQDs-CD and trimesoyl chloride (TMC) on the modified multi-carbon nanotubes (MWCNTs) substrate. The incorporation of NGQDs significantly elevated the rejection (increased by âˆ¼ 45.08%) of the resultant membrane for small molecular dye (Methyl orange, MO) compared to the pristine CD membrane at low pressure (1.5 bar). The newly developed NGQDs-CD-MWCNTs membrane exhibited enhanced water permeability without compromising the dye rejection compared to the pure NGQDs membrane. The improved performance of the membrane was primarily attributed to the synergistic effect of functionalized NGQDs and the special hollow-bowl structure of CD. The optimal NGQDs-CD-MWCNTs-5 membrane expressed pure water permeability of 12.35 L m-2h-1 bar-1 at the pressure of 1.5 bar. Noteworthily, the NGQDs-CD-MWCNTs-5 membrane not only showed high rejection for the larger molecular dye of Congo Red (CR, 99.50%) but also for the smaller molecular dye of MO (96.01%) and Brilliant Green (BG, 95.60%) with the permeability of 8.81, 11.40, and 6.37 L m-2h-1 bar-1, respectively at low pressure (1.5 bar). The rejection of inorganic salts by the NGQDs-CD-MWCNTs-5 membrane was 17.20% for sodium chloride (NaCl), 14.30% for magnesium chloride (MgCl2), 24.63% for magnesium sulfate (MgSO4), and 54.58% for sodium sulfate (Na2SO4), respectively. The great rejection of dyes remained in the dye/salt binary mixed system (higher than 99% for BG and CR, <21% for NaCl). Importantly, the NGQDs-CD-MWCNTs-5 membrane exhibited favorable antifouling performance and potential good operation stability performance. Consequently, the fabricated NGQDs-CD-MWCNTs-5 membrane suggested a prospective application for the reuse of salts and water in textile wastewater treatment owing to the effective selective separation performance.

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