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1.
Small ; 20(11): e2307349, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38105349

RESUMO

Co electroreduction of carbon dioxide and nitrate to synthesize urea provides an alternative strategy to high energy-consumption traditional methods. However, the complexity of the reaction mechanism and the high energy barrier of nitrate reduction result in a diminished production of urea. Herein, a convenient electrodeposition technique to prepare the FeOOH with low spin state iron that increases the yield rate of urea efficiently is employed. According to soft X-ray Absorption Spectroscopy and theoretical calculations, the unique configuration of low spin state iron as electron acceptors can effectively induce electron pair transfer from the occupied σ orbitals of intermediate * NO to empty d orbitals of iron. This σ→d donation mechanism leads to a reduction in the energy barrier associated with the rate-determining step (* NOOH→* NO + * OH), hence augmenting the urea generation. The low spin state iron presents a high urea yield rate of 512 µg h-1  cm-2 , representing approximately two times compared to the medium spin state iron. The key intermediates (* NH2 and * CO) in the formation of C─N bond are detected with in situ Fourier transform infrared spectroscopy. The coupling of * NH2 and * CO contributes to the formation of * CONH2 , which subsequently endures multi-step proton-coupled electron transfer to generate urea.

2.
Small ; 20(23): e2309371, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38169101

RESUMO

Construction of heterojunctions is an effective strategy to enhanced electrocatalytic oxygen evolution reaction (OER), but the structural evolution of the active phases and synergistic mechanism still lack in-depth understanding. Here, an FeOOH/Ni3S2 heterostructure supported on nickel foam (NF) through a two-step hydrothermal-chemical etching method is reported. In situ Raman spectroscopy study of the surface reconstruction behaviors of FeOOH/Ni3S2/NF indicates that Ni3S2 can be rapidly converted to NiOOH, accompanied by the phase transition from α-FeOOH to ß-FeOOH during the OER process. Importantly, a deep analysis of Ni─O bond reveals that the phase transition of FeOOH can regulate the lattice disorder of NiOOH for improved catalytic activity. Density functional theory (DFT) calculations further confirm that NiOOH/FeOOH heterostructure possess strengthened adsorption for O-containing intermediates, as well as lower energy barrier toward the OER. As a result, FeOOH/Ni3S2/NF exhibits promising OER activity and stability in alkaline conditions, requiring an overpotential of 268 mV @ 100 mA cm-2 and long-term stability over 200 h at a current density of 200 mA cm-2. This work provides a new perspective for understanding the synergistic mechanism of heterogeneous electrocatalysts during the OER process.

3.
Small ; 20(20): e2308212, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38100280

RESUMO

The FeOOH/Zn(OH)2/CoS (FZC) nanocomposites are synthesized and show the outstanding electrochemical properties in both supercapacitor and catalytic hydrogen production. The specific area capacitance reaches 17.04 F cm-2, which is more than ten times higher than that of FeOOH/Zn(OH)2 (FZ) substrate: 1.58 F cm-2). FZC nanocomposites also exhibit the excellent cycling stability with an initial capacity retention rate of 93.6% after 10 000 long-term cycles. The electrolytic cell (FZC//FZC) assembled with FZC as both anode and cathode in the UOR (urea oxidation reaction)|| HER (hydrogen evolution reaction) coupled system requires a cell voltage of only 1.453 V to drive a current density of 10 mA cm-2. Especially, the electrochemical performances of FZC nanocomposites are enhanced in magnetic field, and the mechanism is proposed based on Stern double layer model at electrode-electrolyte interface (EEI). More electrolyte ions reach the surface of FZC electrode material under Kelvin force, moreover, the warburg impedance of FZC nanocomposites decrease under magnetic field action, which results in the enhanced behaviors for both the energy storage and urea oxidation reaction .

4.
Small ; 20(35): e2401022, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38809081

RESUMO

Renewable energy technologies, such as water splitting, heavily depend on the oxygen evolution reaction (OER). Nanolaminated ternary compounds, referred to as MAX phases, show great promise for creating efficient electrocatalysts for OER. However, their limited intrinsic oxidative resistance hinders the utilization of conductivity in Mn+1Xn layers, leading to reduced activity. In this study, a method is proposed to improve the poor inoxidizability of MAX phases by carefully adjusting the elemental composition between Mn+1Xn layers and single-atom-thick A layers. The resulting Ta2FeC catalyst demonstrates superior performance compared to conventional Fe/C-based catalysts with a remarkable record-low overpotential of 247 mV (@10 mA cm-2) and sustained activity for over 240 h. Notably, during OER processing, the single-atom-thick Fe layer undergoes self-reconstruction and enrichment from the interior of the Ta2FeC MAX phase toward its surface, forming a Ta2FeC@Ta2C@FeOOH heterostructure. Through density functional theory (DFT) calculations, this study has found that the incorporation of Ta2FeC@Ta2C not only enhances the conductivity of FeOOH but also reduces the covalency of Fe─O bonds, thus alleviating the oxidation of Fe3+ and O2-. This implies that the Ta2FeC@Ta2C@FeOOH heterostructure experiences less lattice oxygen loss during the OER process compared to pure FeOOH, leading to significantly improved stability. These results highlight promising avenues for further exploration of MAX phases by strategically engineering M- and A-site engineering through multi-metal substitution, to develop M2AX@M2X@AOOH-based catalysts for oxygen evolution.

5.
Environ Res ; 257: 119293, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-38838749

RESUMO

Recently, photocatalysis combined peroxydisulfate activation under visible light (PC-PDS/Vis) was developed as a promising technology for removing antibiotics in water. Herein, Mn doped FeOOH (Mn-FeOOH) nanoclusters were grown in-situ on the surface of graphitic carbon nitride nanosheets (CNNS) using a wet chemical method, which served as a visible-light-driven photocatalyst for peroxydisulfate (PDS) activation. Photovoltaic property characterizations revealed that Mn-FeOOH/CNNS owned superior light capture ability and carrier separation efficiency. According to DFT calculations, the synergistic effect between Mn and Fe species was proved to enhance the adsorption and activation of PDS. 99.7% of tetracycline (TC) was rapidly removed in 50 min in the PC-PDS/Vis system. In addition, Mn-FeOOH/CNNS exhibited high recycling stability with low iron leaching, attributed to the interaction between Mn-FeOOH clusters and carbon species. Quenching experiments and electron spin resonance (ESR) tests unveiled that •O2- played a significant role in TC removal, while •OH and SO4•- acted as additional roles contributing to the overall process. These findings given a new strategy for antibiotics degradation by photocatalysis, offering deeper insights for the advancement of sustainable and cutting-edge wastewater treatment technologies.


Assuntos
Grafite , Luz , Tetraciclina , Poluentes Químicos da Água , Tetraciclina/química , Poluentes Químicos da Água/química , Grafite/química , Catálise , Antibacterianos/química , Manganês/química , Sulfatos/química , Compostos de Nitrogênio/química , Ferro/química , Processos Fotoquímicos
6.
Mikrochim Acta ; 191(3): 163, 2024 02 28.
Artigo em Inglês | MEDLINE | ID: mdl-38413431

RESUMO

Carbendazim (CBD) is widely used as a fungicide that acts as a pesticide in farming to prevent crop diseases. However, CBD can remain on crops for a long time. When consumed by humans and animals, it produces a range of toxic symptoms and poses a serious threat to their health. Therefore, the detection of CBD is necessary. Traditional assay strategies for CBD detection, although sensitive and practical, can hardly achieve fast, robust monitoring during food processing and daily life. Here, we designed a novel electrochemical sensor for CBD detection. In this method, iron oxyhydroxide nanomaterial (ß-FeOOH) was first prepared by hydrothermal method. Then, a molecularly imprinted polymer (MIP) layer was electropolymerized on the surface using CBD as the template and resorcinol (RC) as the functional monomer. The synergistic interaction between ß-FeOOH and MIP endows the MIP/ß-FeOOH/CC-based electrochemical sensor with high specificity and sensitivity. Under optimal conditions, the MIP/ß-FeOOH/CC-based sensor showed a wide linear range of 39 pM-80 nM for CBD and a detection limit as low as 25 pM. Therefore, the as-prepared sensor can be a practical and effective tool for pesticide residue detection.


Assuntos
Benzimidazóis , Carbamatos , Compostos Férricos , Impressão Molecular , Polímeros , Animais , Humanos , Polímeros/química , Impressão Molecular/métodos , Polímeros Molecularmente Impressos
7.
J Environ Manage ; 353: 120157, 2024 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-38295639

RESUMO

Nanoscale zerovalent iron (Fe0)-based materials have been demonstrated to be a effective method for the U(VI) removal. However, limited research has been conducted on the long-term immobilization efficiency and mechanism of Fe0-based materials for U(VI), which are essential for achieving safe handling and disposal of U(VI) on a large scale. In this study, the prepared carboxymethyl cellulose (CMC) and sulfurization dual stabilized Fe0 (CMC-Fe0/FeS) exhibited excellent long-term immobilization performances for U(VI) under both anoxic and oxic conditions, with the immobilization efficiencies were respectively reached over 98.0 % and 94.8 % after 180 days of aging. Most importantly, different from the immobilization mechanisms of the fresh CMC-Fe0/FeS for U(VI) (the adsorption effect of -COOH and -OH groups, coordination effect with sulfur species, as well as reduction effect of Fe0), the re-mobilized U(VI) were finally re-immobilized by the formed FeOOH and Fe3O4 on the aged CMC-Fe0/FeS. Under anoxic conditions, more Fe3O4 was produced, which may be the main reason for the long-term immobilization U(VI). Under oxic conditions, the production of Fe3O4 and FeOOH were relatively high, which both played significant roles in re-immobilizing U(VI) through surface complexation, reduction and incorporation effects.


Assuntos
Urânio , Carboximetilcelulose Sódica , Ferro , Adsorção
8.
Molecules ; 29(12)2024 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-38930978

RESUMO

Developing a low-cost and highly efficient semiconductor photocatalyst for the decomposition of organic pollutants and antibiotics is highly desirable. Herein, FeOOH nanosheets were prepared using a liquid-phase stirring technique and combined with ZnCdS (ZCS) nanoparticles to construct FeOOH/ZCS nanocomposite photocatalysts. The photocatalytic efficiency of the FeOOH/ZCS nanocomposite was evaluated for the decomposition of various pollutants, including rhodamine B, methylene Blue, and tetracycline. The FeOOH/ZCS nanocomposite exhibited significantly higher photocatalytic performance for the decomposition of various organics. Moreover, the optimized FeOOH/ZCS retained more than 90% of its initial photocatalytic activity even after five successful runs. Radical quenching test and electron spin resonance (ESR) analysis revealed that hydroxyl radicals (•OH) play a dominant role for the decomposition of organics. The FeOOH/ZCS Z-scheme heterojunction significantly facilitates higher charge transfer efficiency and the generation of reactive radicals, resulting in excellent photocatalytic degradation performance. This work offers a new approach to synthesis FeOOH-based photocatalyst for the elimination of organics and antibiotics in water.

9.
Molecules ; 29(13)2024 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-38999155

RESUMO

The composite photocatalyst FeOOH/g-C3N4 was prepared through thermal polycondensation and co-precipitation methods, followed by XRD, SEM and UV-vis characterization. The stability of FeOOH/g-C3N4 was explored by the recycling test. The active species in the reaction system were investigated by the capture experiment. The results indicated that the optimal preparation condition for g-C3N4 involved calcination at 600 °C for 4 h. XRD analysis revealed that g-C3N4 exhibits a high-purity phase, and Fe in FeOOH/g-C3N4 exists in a highly dispersed amorphous state. SEM analysis showed that FeOOH/g-C3N4 has a rough surface with an irregular layered structure. Element composition analysis confirmed that the content of elements in the prepared catalyst is consistent with the theoretical calculation. FeOOH/g-C3N4 possesses the largest specific surface area of 143.2 m2/g and a suitable pore distribution. UV-vis DRS analysis showed that the absorption intensity of FeOOH/g-C3N4 is stronger than that of g-C3N4. When the catalyst dosage was 1.0 g/L, the H2O2 dosage was 4 mmol/L, the PNP initial concentration was 10 mg/L and the initial pH value was 5, the PNP removal could reach 92% in 120 min. Even after 5 cycles, the efficiency of PNP removal by FeOOH/g-C3N4 remains nearly 80%. The capture experiment indicated that both •OH and •O2- play roles in the photocatalytic degradation of PNP, with •OH being more significant. These findings affirm that FeOOH has been successfully incorporated into g-C3N4, resulting in a conspicuous catalytic effect on the degradation of PNP in the visible light-assisted Fenton-like reaction.

10.
Molecules ; 29(4)2024 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-38398669

RESUMO

In this work, to promote the separation of photogenerated carriers, prevent the catalyst from photo-corrosion, and improve the photo-Fenton synergistic degradation of organic pollutants, the coating structure of FeOOH/BiO2-x rich in oxygen vacancies was successfully synthesized by a facile and environmentally friendly two-step process of hydrothermal and chemical deposition. Through a series of degradation activity tests of synthesized materials under different conditions, it was found that FeOOH/BiO2-x demonstrated outstanding organic pollutant degradation activity under visible and near-infrared light when hydrogen peroxide was added. After 90 min of reaction under photo-Fenton conditions, the degradation rate of Methylene Blue by FeOOH/BiO2-x was 87.4%, significantly higher than the degradation efficiency under photocatalysis (60.3%) and Fenton (49.0%) conditions. The apparent rate constants of FeOOH/BiO2-x under photo-Fenton conditions were 2.33 times and 3.32 times higher than photocatalysis and Fenton catalysis, respectively. The amorphous FeOOH was tightly coated on the layered BiO2-x, which significantly increased the specific surface area and the number of active sites of the composites, and facilitated the improvement of the separation efficiency of the photogenerated carriers and the prevention of photo-corrosion of BiO2-x. The analysis of the mechanism of photo-Fenton synergistic degradation clarified that ·OH, h+, and ·O2- are the main active substances involved in the degradation of pollutants. The optimal degradation conditions were the addition of the FeOOH/BiO2-x composite catalyst loaded with 20% Fe at a concentration of 0.5 g/L, the addition of hydrogen peroxide at a concentration of 8 mM, and an initial pH of 4. This outstanding catalytic system offers a fresh approach to the creation and processing of iron-based photo-Fenton catalysts by quickly and efficiently degrading various organic contaminants.

11.
Small ; 19(22): e2208232, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-36871148

RESUMO

Graphite phased carbon nitride (g-C3 N4 ) has attracted extensive attention attributed to its non-toxic nature, remarkable physical-chemical stability, and visible light response properties. Nevertheless, the pristine g-C3 N4 suffers from the rapid photogenerated carrier recombination and unfavorable specific surface area, which greatly limit its catalytic performance. Herein, 0D/3D Cu-FeOOH/TCN composites are constructed as photo-Fenton catalysts by assembling amorphous Cu-FeOOH clusters on 3D double-shelled porous tubular g-C3 N4 (TCN) fabricated through one-step calcination. Combined density functional theory (DFT) calculations, the synergistic effect between Cu and Fe species could facilitate the adsorption and activation of H2 O2 , and the separation and transfer of photogenerated charges effectively. Thus, Cu-FeOOH/TCN composites acquire a high removal efficiency of 97.8%, the mineralization rate of 85.5% and a first-order rate constant k = 0.0507 min-1 for methyl orange (MO) (40 mg L-1 ) in photo-Fenton reaction system, which is nearly 10 times and 21 times higher than those of FeOOH/TCN (k = 0.0047 min-1 ) and TCN (k = 0.0024 min-1 ), respectively, indicating its universal applicability and desirable cyclic stability. Overall, this work furnishes a novel strategy for developing heterogeneous photo-Fenton catalysts based on g-C3 N4 nanotubes for practical wastewater treatment.

12.
Small ; 19(33): e2301255, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37086139

RESUMO

The electronic regulation and surface reconstruction of earth-abundant electrocatalysts are essential to efficient oxygen evolution reaction (OER). Here, an inverse-spinel Co,S atomic pair codoped Fe3 O4 grown on iron foam (Co,S-Fe3 O4 /IF) is fabricated as a cost-effective electrocatalyst for OER. This strategy of Co and S atomic pair directional codoping features accelerates surface reconstruction and dynamically stabilizes electronic regulation. CoS atomic pairs doped in the Fe3 O4 crystal favor controllable surface reconstruction via sulfur leaching, forming oxygen vacancies and Co doping on the surface of reconstructed FeOOH (Co-FeOOH-Ov /IF). Before and after surface reconstruction via in situ electrochemical process, the Fe sites with octahedral field dynamically maintains an appropriate electronic structure for OER intermediates, thus exhibiting consistently excellent OER performance. The electrochemically tuned Fe-based electrodes exhibit a low overpotential of 349 mV at a current density of 1000 mA cm-2 , a slight Tafel slope of 43.3 mV dec-1 , and exceptional long-term electrolysis stability of 200 h in an alkaline medium. Density functional theory calculations illustrate the electronic regulation of Fe sites, changes in Gibbs free energies, and the breaking of the restrictive scaling relation between OER intermediates. This work provides a promising directional codoping strategy for developing precatalysts for large-scale water-splitting systems.

13.
Chemistry ; 29(6): e202203033, 2023 Jan 27.
Artigo em Inglês | MEDLINE | ID: mdl-36310518

RESUMO

At near neutral to basic pH, hydrolysis-induced aggregation to insoluble bulk iron-oxide is often regarded as the pitfalls of molecular iron clusters. Iron-oxide nanocrystals are encouragingly active over the molecular clusters and/or bulk oxides albeit, stabilizing such nanostructures in aqueous pH and under turnover condition remain a perdurable challenge. Herein, an Anderson-type [Mo7 O24 ]6- isopolyanion, a small (dimension ca. 0.85 nm) isolable polyoxometalate (POM) possessing only {31} atoms, has been introduced for the first time as a covalent linker to stabilize an infinitely stable and aqueous-soluble γ-FeO(OH) nanocore. During the hydrothermal isolation of the material, a partial dissociation of the parent [Mo7 O24 ]6- may lead to the in situ generation of few analogous [Mox Oy ]n- clusters, proved by Raman study, which can also participate in stabilizing the γ-FeO(OH) nanocore, Mox Oy @FeO(OH). However, due to high ionic charge on {Mo=O} terminals of the [Mox Oy ]n- , they are covalently linked via MoVI -µ2 O-FeIII bridging to γ-FeO(OH) core in Mox Oy @FeO(OH), established by numerous spectroscopic and microscopic evidence. Such bonding mode is more likely as precedent from the coordination motif documented in the transition metal clusters stabilized by this POM. The γ-FeO(OH) nanocore of Mox Oy @FeO(OH) behaves as potent active center for electrochemical water oxidation with a overpotential, 263 mV @ 10 mA cm-2 , lower than that observed for bare γ-FeO(OH). Despite of some molybdenum dissolution from the POM ligands to the electrolyte, residual anionic POM fragments covalently bound to the OER active γ-FeO(OH) core of the Mox Oy @FeO(OH) makes the surface predominantly ionic that results in an ordered electrical double layer to promote a better charge transport across the electrode-electrolyte junction, less likely in bulk γ-FeO(OH).

14.
Nanotechnology ; 34(32)2023 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-37163997

RESUMO

Transition metal sulfides (TMSs) for electrochemical water splitting undergo significant self-reconstruction to form actual active species favorable for high oxygen evolution reaction (OER) performance. However, the complete self-reconstruction of most reported TMSs in alkaline media is unfrequent and the active species cannot be efficiently used. Herein, self-supported FeS2/NiS2nanosheet arrays (FeNiS) are deliberately fabricated as pre-catalysts and then accomplished deep phase transformation into low-crystalline and ultrathin FeOOH/NiOOH (FeNiS-R) nanosheets favorable to alkaline OER. Variousex situcharacterization studies uncover that the FeNiS-R with abundant interfaces is generated via complete reconstruction during electrolysis and the high-valence Fe and Ni in the FeNiS-R interface are the real active sites for high OER activity. The reconstructed FeNiS-R exhibits a small overpotential of 290 mV at 100 mA cm-2and favorable durability (≥80 h), much superior to commercial benchmark IrO2. This work provides a promising avenue to achieve the deep reconstruction of TMSs and the targeted design of OER catalysts in energy devices.

15.
Bull Environ Contam Toxicol ; 110(3): 57, 2023 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-36800098

RESUMO

Biotic transformation of imidacloprid (IMD) has been widely investigated in the environments. However, little was known about IMD degradation via abiotic pathways, such as reactive oxygen species (ROS)-based oxidation processes. Here we systematically investigated the mechanism of hydroxyl radical (•OH) production and the associated IMD degradation in the goethite (α-FeOOH)-based Fenton-like systems. Results showed that IMD can be efficiently degraded in the α-FeOOH/H2O2 systems, with degradation rate exceeded 80% within 48 h. Based on the examination of electron paramagnetic resonance (EPR) and chemical probes, •OH was identified as the key ROS that responsible for IMD degradation. IMD can be decomposed via hydroxylation or removal of -N-NO2 to produce hydroxylated IMD, cyclic urea and 6-chloronicotinic acid, with the associated toxicities also evaluated. In addition, the increasing H2O2 concentration and decreasing solution pH both significantly increased IMD degradation. This study provides theoretical understanding for the implications of soil mineral-based Fenton-like reactions in the abiotic transformation of pesticide pollutants.


Assuntos
Peróxido de Hidrogênio , Ferro , Espécies Reativas de Oxigênio , Minerais , Oxirredução
16.
Environ Sci Technol ; 56(9): 5542-5551, 2022 05 03.
Artigo em Inglês | MEDLINE | ID: mdl-35412804

RESUMO

Sulfidation can greatly improve the efficiency of utilization of reducing equivalents for contaminant removal; however, whether this method benefits Fenton-like reactions or not and the possible mechanism are not well understood. In this study, we revealed that surface sulfidation can greatly promote the heterogeneous Fenton activity of ß-FeOOH (Fe3S4@ß-FeOOH) by 40 times, in which not only the •OH formation was enhanced but also SO4•- as a new oxidation species was generated. Moreover, their contribution to metronidazole (MTZ) degradation was 52.5 and 37.1%, respectively. In comparison, almost no HO2•/O2•- was detected in the Fe3S4@ß-FeOOH/H2O2 system. These results were different from some previously reported Fenton counterparts. Based on the characterization and probe experiments, sulfur species, including S2-, S0, and Sn2-, as an electron donor and electron shuttle were responsible for efficient conversion of Fe(III) into Fe(II) other than via the Haber-Weiss mechanism, leading to excellent •OH generation via a Fenton-like mechanism. Most importantly, HSO5- can be generated from SO32- oxidized by •OH, and its scission into SO4•- was not dependent on the extra electric potential or Fe-O2-S(IV) intermediate. These findings provided new insight for utilizing sulfidation to improve the activity of iron-based Fenton catalysts.


Assuntos
Compostos Férricos , Peróxido de Hidrogênio , Ferro , Oxirredução , Sulfatos
17.
Environ Sci Technol ; 56(7): 4542-4552, 2022 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-35316022

RESUMO

The integrated system of gas-phase advanced oxidation process combined with sulfite-based wet absorption process is a desirable method for simultaneous removal of SO2, NO, and Hg0, but due to the enrichment of nitrite and Hg2+, resourcing harmless wastewater is still a challenge. To tackle this problem, this study fabricated a bifunctional ß-FeOOH@MXene heterogeneous Fenton material, of which the crystalline phase, morphology, structure, and composition were revealed by using X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy-energy dispersive x-ray spectroscopy, and transmission electron microscopy. It exhibits excellent performance on nitrite oxidation (99.5%) and Hg2+ removal (99.7%) and can maintain stable outstanding ability after 13 cycles, with superior Hg2+ adsorption capacity (395 mg/g) and ultralow Fe leaching loss (<0.018 wt %). The synergism between MXene and ß-FeOOH appears as follows: (i) MXene, as an inductive agent, directionally converted Fe2O3 into ß-FeOOH in the hydrothermal method and greatly reduced its monomer size; (ii) the introduced ≡Ti(III)/≡Ti(II) accelerated the regeneration of ≡Fe(II) via rapid electron transfer, thereby improving the heterogeneous Fenton reaction; and (iii) MXene strongly immobilized ß-FeOOH to greatly inhibit Fe-leaching. HO•, •O2--, and 1O2 were the main radicals identified by electron spin resonance. Radical quenching tests showed their contributions to NO2- oxidation in the descending order HO• > 1O2 > •O2-. Quantum chemical calculations revealed that •OH-induced oxidation of NO2- or HNO2 was the primary reaction path. Density functional theory calculations combined with X-ray photoelectron spectroscopy and Raman characterizations displayed the Hg2+ removal mechanism, with Hg2Cl2, HgCl2, and HgO as the main byproducts. This novel material provides a new strategy for resourcing harmless wastewater containing nitrite and Hg2+.

18.
Environ Res ; 214(Pt 3): 113964, 2022 11.
Artigo em Inglês | MEDLINE | ID: mdl-35944621

RESUMO

In this study, activation of peroxymonosulfate (PMS) by amorphous FeOOH to degrade sulfamethoxazole (SMX) was investigated. The amorphous FeOOH showed a better performance in the decomposition of PMS and the degradation of SMX than the crystallized α-FeOOH and ß-FeOOH. The quenching experiments and EPR measurements suggested that the mechanism of PMS activation by amorphous FeOOH was mainly the surface-bound radicals (●OH and SO4●-). Basically, the surface-bound ●OH radicals were the dominate reactive oxide species in this system, which were mainly generated via the decomposition of amorphous FeOOH-PMS complexes. The degradation of SMX was significantly inhibited with the presence of H2PO4-, and this adverse impact was negligibly affected by the increase of H2PO4- concentration, implying that the inhibition of SMX degradation was caused by competitive adsorption. Consequently, the Fe-OH bonds on the amorphous FeOOH were proposed as the reactive sites for forming amorphous FeOOH-PMS complexes. Besides, the amorphous FeOOH showed a better performance in the degradation of SMX in the acid conditions than that in the base conditions due to the surface charge of amorphous FeOOH. More importantly, the reduction efficiency of Fe(III) was significantly enhanced due to the excellent conductivity of amorphous FeOOH.


Assuntos
Sulfametoxazol , Poluentes Químicos da Água , Elétrons , Compostos Férricos , Radical Hidroxila/química , Peróxidos , Poluentes Químicos da Água/química
19.
Environ Res ; 215(Pt 1): 114233, 2022 12.
Artigo em Inglês | MEDLINE | ID: mdl-36058268

RESUMO

A novel 3D α-FeOOH@MoS2/rGO nanocomposite was successfully fabricated by a simple in situ hydrothermal method. It is a highly efficient heterogeneous catalyst in activation of peroxymonosulfate (PMS) for rapid degradation of rhodamine B (RhB), with 99.9% of RhB removed within 20 min. The introduction of rGO contributes to uniform dispersion and sufficient contact of α-FeOOH and MoS2 nanosheets. Highly active Mo(IV) enhances the reduction of Fe(III), improves Fe(III)/Fe(II) conversion and promotes the generation of O21, which ensures an improved catalytic activity. MoS2/rGO hybrid can effectively solve the problem of material reunion and make α-FeOOH exhibit excellent catalytic performance. The α-FeOOH@MoS2-rGO/PMS system is a co-catalytic system based on the active components of α-FeOOH and MoS2. The main reactive oxygen species in the α-FeOOH@MoS2-rGO/PMS system are O21, SO4.- and ⋅O2-, which contribute to a high reactivity over a wide range of pH (5-9). Besides, this system is highly resistant to anions (Cl-, SO42-) and natural organic matter (humic acid), and can be widely used for degradation of common organic pollutants. The α-FeOOH@MoS2/rGO is a promising Fenton-like catalyst for refractory organic wastewater treatment.


Assuntos
Poluentes Ambientais , Grafite , Nanocompostos , Catálise , Compostos Ferrosos , Substâncias Húmicas , Ferro , Compostos de Ferro , Minerais , Molibdênio , Peróxidos , Espécies Reativas de Oxigênio
20.
Mikrochim Acta ; 189(2): 58, 2022 01 11.
Artigo em Inglês | MEDLINE | ID: mdl-35013820

RESUMO

Immunochromatography testing strips (ICTs) promise to become the point-of-care test format for early diagnosis due to their convenience, low cost, and simplification. However, the insufficient signal intensity and limited sensitivity of this format hamper their application. Herein, we overcame these limitations by integrating rod-like ferric oxyhydroxide (ß-FeOOH) nanoparticles with ICTs. By varying the concentration of PEI, a one-pot, mild-temperature hydrolysis method was adapted for the synthesis and morphology regulation of ß-FeOOH nanorod. Due to the excellent enzyme-like catalytic activity toward peroxidase substrates (TMB) in the presence of hydrogen peroxide (H2O2), the ß-FeOOH nanorod in ICTs served as a signal generator and the nanozyme for signal amplification. The proof-of-concept work was performed for the detection of human chorionic gonadotropin (hCG). A two fold improvement of detection sensitivity was achieved compared to the sensitivity of conventional Au NPs-based ICTs. These results show that ß-FeOOH-based ICT has a potential application in POCT detection in clinical diagnostics.


Assuntos
Gonadotropina Coriônica/química , Cromatografia de Afinidade/instrumentação , Compostos Férricos/química , Nanotubos/química , Peroxidase/metabolismo , Cromatografia de Afinidade/métodos , Peroxidase/química , Sensibilidade e Especificidade , Temperatura
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