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1.
J Environ Sci (China) ; 149: 535-550, 2025 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-39181665

RESUMO

Li6ZnO4 was chemically modified by nickel addition, in order to develop different compositions of the solid solution Li6Zn1-xNixO4. These materials were evaluated bifunctionally; analyzing their CO2 capture performances, as well as on their catalytic properties for H2 production via dry reforming of methane (DRM). The crystal structures of Li6Zn1-xNixO4 solid solution samples were determined through X-ray diffraction, which confirmed the integration of nickel ions up to a concentration around 20 mol%, meanwhile beyond this value, a secondary phase was detected. These results were supported by XPS and TEM analyses. Then, dynamic and isothermal thermogravimetric analyses of CO2 capture revealed that Li6Zn1-xNixO4 solid solution samples exhibited good CO2 chemisorption efficiencies, similarly to the pristine Li6ZnO4 chemisorption trends observed. Moreover, a kinetic analysis of CO2 isothermal chemisorptions, using the Avrami-Erofeev model, evidenced an increment of the constant rates as a function of the Ni content. Since Ni2+ ions incorporation did not reduce the CO2 capture efficiency and kinetics, the catalytic properties of these materials were evaluated in the DRM process. Results demonstrated that nickel ions favored hydrogen (H2) production over the pristine Li6ZnO4 phase, despite a second H2 production reaction was determined, methane decomposition. Thereby, Li6Zn1-xNixO4 ceramics can be employed as bifunctional materials.


Assuntos
Dióxido de Carbono , Hidrogênio , Metano , Hidrogênio/química , Metano/química , Dióxido de Carbono/química , Níquel/química , Catálise , Modelos Químicos
2.
Nano Lett ; 2024 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-39356732

RESUMO

Chemisorption on organometallic-based adsorbents is crucial for the controlled separation and purification of targeted systems. Herein, oriented 1D NH2-CuBDC·H2O metal-organic frameworks (MOFs) featuring accessible CuII sites are successfully fabricated by bottom-up interfacial polymerization. The prepared MOFs, as deliberately self-assembled secondary particles, exhibit a visually detectable coordination-responsive characteristic induced by the nucleophilic substitution and competitive coordination of guest molecules. As a versatile phase-change chemosorbent, the MOFs exhibit unprecedented NH3 capture (18.83 mmol g-1 at 298 K) and bioethanol dehydration performance (enriching ethanol from 99% to 99.99% within 10 min by direct adsorption separation of liquid mixtures of ethanol and water). Furthermore, the raw materials for preparing the 1D MOFs are inexpensive and readily available, and the facile regeneration with water washing at room temperature effectively minimizes the energy consumption and cost of recycling, enabling it to be the most valuable adsorbent for the removal and separation of target substances.

3.
Int J Biol Macromol ; 279(Pt 4): 135600, 2024 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-39276899

RESUMO

The rapid industrial progress in today's world has led to an alarming increase in water pollution caused by various contaminants such as synthetic dyes. To address this issue, a new hydrogel sorbent, BC-r-Na-Alg-g-p(NIPAm-co-AAc), was developed by combining bentonite clay, sodium alginate, and poly(N-isopropyl acrylamide-co-acrylic acid) through one-pot free radical polymerization at 60 °C. The developed sorbent was characterized using several analytical techniques including SEM, FTIR, TGA, UTM, and swelling studies. The swelling capacity of the sorbent was observed to increase remarkably with an increase in pH, reaching a maximum of 9664 % at pH 11. In batch mode sorption experiments, the sorbent's performance toward methylene green (MG) was investigated by analysing the effects of contact time, pH, temperature, and concentration. The experimental data were fitted to pseudo-second-order kinetic and Langmuir isotherm models, indicating chemisorption as the dominant interaction mode between the anionic sorbent and cationic MG. However, physisorption may also occur to a lesser extent, indicated by the significant R2 of the pseudo-first-order kinetic and Freundlich isotherm models. Additionally, the sorbent exhibited very little decrease (approximately 5 %) in sorptive performance for six sorption-desorption cycles. Overall, the facile fabrication, excellent swelling (9664 %), promising sorption performance (2573 mg.g-1), and good recyclability (6 cycles) make the developed sorbent a potential candidate for various industrial applications.


Assuntos
Alginatos , Bentonita , Argila , Hidrogéis , Azul de Metileno , Poluentes Químicos da Água , Bentonita/química , Alginatos/química , Hidrogéis/química , Adsorção , Concentração de Íons de Hidrogênio , Poluentes Químicos da Água/química , Poluentes Químicos da Água/isolamento & purificação , Argila/química , Azul de Metileno/química , Cinética , Temperatura , Purificação da Água/métodos
4.
Int J Biol Macromol ; 280(Pt 2): 135881, 2024 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-39321518

RESUMO

Adsorbent materials constructed from natural macromolecular products are favored because of their wide range of sources, biodegradability, and environmental friendliness. Salecan is a novel extracellular polysaccharide with ideal physicochemical and biological activities. Here, we have designed a polymer gel through UV-initiated polymerization of [2-(Methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (SBMA) in the mixture of salecan and tannic acid. Photopatterned polymerization process allowed in situ formation of gel adsorbent in a mild reaction condition with energy-efficient manner. Batch experiments for toluidine blue (TB) adsorption were carried out as a function of initial dye concentration, solution pH, contact time, and gel dosage to examine the adsorption capacity, potential mechanism, and removal efficiency. Adsorption behavior exhibited a pH-dependence pattern, which was closely related to their swelling and morphological properties. Adsorption process was in conformity to pseudo-second-order kinetic and Langmuir isotherm models, unlocking a chemical adsorption behavior and monolayer-type removal. The maximum adsorption was 490.2 mg/g, which could be considered a superiorly competing value. Additionally, the UV-gel still showed desirable recyclability and maintained the adsorption effectiveness over 95 % after five regeneration cycles. This study opened up new prospects in preparing high performance adsorbent for TB decontamination and laid the foundation for polysaccharide-based adsorption material research.

5.
Angew Chem Int Ed Engl ; : e202412939, 2024 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-39115106

RESUMO

Hole-collecting monolayers have greatly advanced the development of positive-intrinsic-negative perovskite solar cells (p-i-n PSCs). To date, however, most of the anchoring groups in the reported monolayer materials are designed to bind to the transparent conductive oxide (TCO) surface, resulting in less availability for other functions such as tuning the wettability of the monolayer surface. In this work, we developed two anchorable molecules, 4PATTI-C3 and 4PATTI-C4, by employing a saddle-like indole-fused cyclooctatetraene as a π-core with four phosphonic acid anchoring groups linked through propyl or butyl chains. Both molecules form monolayers on TCO substrates. Thanks to the saddle shape of a cyclooctatetraene skeleton, two of the four phosphonic acid anchoring groups were found to point upward, resulting in hydrophilic surfaces. Compared to the devices using 4PATTI-C4 as the hole-collecting monolayer, 4PATTI-C3-based devices exhibit a faster hole-collection process, leading to higher power conversion efficiencies of up to 21.7 % and 21.4 % for a mini-cell (0.1 cm2) and a mini-module (1.62 cm2), respectively, together with good operational stability. This work represents how structural modification of multipodal molecules could substantially modulate the functions of the hole-collecting monolayers after being adsorbed onto TCO substrates.

6.
J Colloid Interface Sci ; 678(Pt A): 393-406, 2024 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-39213992

RESUMO

With the rapid development of large-scale clean energy, lithium-sulfur (Li-S) batteries are considered to be one of the most promising energy storage devices. In this manuscript, the polymetallic hetero-nanocrystal of iron nickel@cobalt nitride encapsulating into boron carbonitride nanotubes (Fe0.64Ni0.36@Co5.47N@BCN) was designed and optimized for use as a modified material for commercial polypropylene (PP) separators. The prepared Fe0.64Ni0.36@Co5.47N@BCN-12 hybrid material presents strong chemisorption and catalytic conversion capabilities, which endows the Fe0.64Ni0.36@Co5.47N@BCN-12//PP separator with enhanced polysulfide shuttling inhibition. The assembled Li-S cells with Fe0.64Ni0.36@Co5.47N@BCN-12//PP separators have minimized charge transfer resistance and faster redox kinetics. Additionally, cells with Fe0.64Ni0.36@Co5.47N@BCN-12//PP separator provide high reversible capacity of 674 mAh/g for 400 cycles at 0.5C and excellent cyclability for 1000 cycles at 2C with a low decay rate of 0.05 % per cycle. Therefore, this study provides a feasible functionalization route for improving the electrochemical performance of Li-S batteries through separator modification.

7.
Environ Res ; 260: 119604, 2024 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-39002636

RESUMO

Fluoride pollution and water scarcity are urgent issues. Reducing fluoride concentration in water is crucial. Kaolinite has been used to study adsorption and fluoride removal in water and to characterize material properties. The experimental results showed that the adsorption capacity of kaolinite decreased with increasing pH. The highest adsorption of fluoride occurred at pH 2, with a capacity of 11.1 mg/g. The fluoride removal efficiency remained high after four regeneration cycles. The fitting results with the Freundlich isotherm model and the external diffusion model showed that the non-homogeneous adsorption of kaolinite fit the adsorption behavior better. Finally, the adsorption mechanism was analyzed by FT-IR and XPS. The binding energies of various adsorption sites and the chemical adsorption properties of atomic states were discussed in relation to DFT calculations. The results showed that Al and H sites were the main binding sites, and the bonding stability for different forms of fluoride varies, with the size of Al-F (-7.498 eV) > H-F (-6.04 eV) > H-HF (-3.439 eV) > Al-HF (-3.283 eV). Furthermore, the density of states and Mulliken charge distribution revealed that the 2p orbital of F was found to be active in the adsorption process and was the main orbital for charge transfer.


Assuntos
Fluoretos , Caulim , Águas Residuárias , Poluentes Químicos da Água , Fluoretos/química , Fluoretos/análise , Caulim/química , Águas Residuárias/química , Adsorção , Poluentes Químicos da Água/química , Poluentes Químicos da Água/análise , Metalurgia , Teoria da Densidade Funcional , Eliminação de Resíduos Líquidos/métodos , Purificação da Água/métodos , Concentração de Íons de Hidrogênio
8.
ACS Nano ; 18(35): 24012-24023, 2024 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-39033415

RESUMO

For highly active electron transfer and ion diffusion, controlling the surface wettability of electrically and thermally conductive 3D graphene foams (3D GFs) is required. Here, we present ultrasimple and rapid superwettability switching of 3D GFs in a reversible and reproducible manner, mediated by solvent-exclusive microwave arcs. As the 3D GFs are prepared with vapors of nonpolar acetone or polar water exclusively, short microwave radiation (≤10 s) leads to plasma hotspot-mediated production of methyl and hydroxyl radicals, respectively. Upon immediate radical chemisorption, the 3D surfaces become either superhydrophobic (water contact angle = ∼170°) or superhydrophilic (∼0°), and interestingly, the wettability transition can be repeated many times due to the facile exchange between previously chemisorbed and newly introduced radicals via the formation of methanol-like intermediates. When 3D GFs of different surficial polarities are incorporated into electric double-layer capacitors with nonpolar ionic liquids or polar aqueous electrolytes, the polarity matching between graphene surfaces and electrolytes results in ≥548.0 times higher capacitance compared to its mismatching at ≥0.5 A g-1, demonstrating the significance of wettability-controlled 3D GFs.

9.
Chemistry ; 30(48): e202402137, 2024 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-38924754

RESUMO

A supramolecular complexation approach is developed to improve the CO2 chemisorption performance of solvent-lean amine sorbents. Operando spectroscopy techniques reveal the formation of carbamic acid in the presence of a crown ether. The reaction pathway is confirmed by theoretical simulation, in which the crown ether acts as a proton acceptor and shuttle to drive the formation and stabilization of carbamic acid. Improved CO2 capacity and diminished energy consumption in sorbent regeneration are achieved.

10.
Chemosphere ; 362: 142633, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38906187

RESUMO

Given the growing concern over the deployment of toxic chemicals in warfare, the rapid and accurate removal and detection of cyanogen chloride (CK) as a blood agent has become increasingly critical. However, conventional physisorbents and chemisorbents used in military respirators are insufficient for the effective removal of CK. In this study, we demonstrate the chemisorption and sensing abilities of Co2(m-DOBDC) (m-DOBDC4- = 4,6-dioxo-1,3-benzenedicarboxylate) for CK via electrophilic aromatic substitution (EAS) in humid environments. Unlike the chemisorption in triethylenediamine (TEDA) impregnated carbon materials, which generates by-products through hydrolysis, the electron-rich C5 sites in m-DOBDC4- ligands give rise to cyano substitution with CK. This leads to the formation of stable C-C bonds and chloride ions (Cl-) coordinating with open Co2+ sites. Such a mechanism prevents the generation of toxic by-products like cyanic acid and hydrochloric acid. Breakthrough experiments conducted in a packed-bed system conclusively demonstrated the superior CK removal capacity of Co2(m-DOBDC) (1662 min/g), compared to TEDA-impregnated activated carbon (323 min/g) under humid conditions. Considering that MOF-74 series, isostructural with Co2(m-DOBDC), barely adsorb CK under similar conditions, this finding marks a significant advancement in developing novel sorbents for CK removal. Moreover, this chemisorption not only exhibited rapid and highly efficient CK removal but also enabled colorimetric monitoring via the distinctive color change induced by the coordination of Cl- acting as σ donors. These findings facilitate the development of adsorption and sensing equipment to protect military personnel from toxic chemical threats.


Assuntos
Colorimetria , Estruturas Metalorgânicas , Nitrilas , Adsorção , Estruturas Metalorgânicas/química , Nitrilas/química , Nitrilas/análise , Cianetos/análise , Cianetos/química
11.
Chemphyschem ; 25(15): e202400209, 2024 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-38863367

RESUMO

This study reveals that, when two hydrogen atoms are produced on the surface of a catalyst (e. g., a metal nanoparticle) upon dissociation of a parahydrogen molecule, their initial nuclear spin correlation can propagate in a branching-chain fashion as they diffuse and combine with random H atoms to produce H2 molecules, which subsequently dissociate. This process leads to a gradual dilution of the non-equilibrium nuclear spin order, but the number of involved H atoms that share the spin order becomes larger. These conclusions, confirmed by the spin density matrix calculations, may be relevant in the context of parahydrogen-induced polarization (PHIP) in heterogeneous hydrogenations catalyzed by supported metal catalysts, the observation of which apparently contradicts the accepted non-pairwise mechanism of the addition of hydrogen to an unsaturated substrate over such catalysts. The potential consequences of the reported findings are discussed in the context of PHIP effects and beyond.

12.
Water Res ; 257: 121708, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38723355

RESUMO

The ammonia recovery from wastewater via electrochemical technologies represents a promising way for wastewater treatment, resource recovery, and carbon emissions reduction. However, chemicals consumption and reactors scalability of the existing electrochemical systems have become the key challenges for their development and application. In this study, a stacked transmembrane electro-chemisorption (sTMECS) system was developed to utilize authigenic acid and base on site for enhancing ammonia recovery from wastewater. The easily scaled up system was achieved via innovatively connecting the cathode chamber in a unit with the anode chamber in the adjacent unit by a hydrophobic gas permeable membrane (GPM). Thus, authigenic base at cathodes and authigenic acid at anodes could be utilized as stripper and absorbent on site to enhance the transmembrane chemisorption of ammonia. Continuous power supply, reducing the distances of electrodes to GPM and moderate aeration of the catholyte could promote ammonia recovery. Applied to the ammonia recovery from the simulated urine, the sTMECS under the current density 62.5 A/cm2 with a catholyte aeration rate of 3.2 L/(L⋅min) for operation time 4 h showed the transmembrane ammonia flux of 26.00 g N/(m2·h) and the system energy consumption of 10.5 kWh/kg N. Accordingly, the developed sTMECS system with chemicals saving, easy scale-up and excellent performance shows good prospects in recovering ammonia from wastewater.


Assuntos
Amônia , Interações Hidrofóbicas e Hidrofílicas , Águas Residuárias , Águas Residuárias/química , Membranas Artificiais , Eliminação de Resíduos Líquidos/métodos , Eletrodos , Técnicas Eletroquímicas , Purificação da Água/métodos
13.
ACS Appl Mater Interfaces ; 16(19): 24473-24482, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38695531

RESUMO

The ability to exfoliate transition metal diborides has led to a renewed interest in their prospect to be applied as catalysts for electrochemical reactions. This is due to an enhanced access to the unprecedented interfaces these nanomaterials offer. In this work, we show that nanosheets exfoliated from TiB2 exhibit vacancies that facilitate an excellent interface for catalyzing nitrogen reduction reaction (NRR). We found that these nanosheets demonstrate a high selectivity toward NH3 because of their abiity to preferentially chemisorb and activate N2. These nanosheets exhibit a superlative NH3 yield of 318 µg h-1 cm-2 at -0.2 V versus RHE with a faradaic efficiency of 57%. We also found how the relative ratios of Ti and B atoms in these nanosheets can affect the NH3 yield and faradaic efficiency. We supplement these results with DFT studies that indicate that it is the creation of frustrated Lewis pairs along with the Ti-B synergy that induces a push-and-pull effect; this in turn favors N2 activation and lowers the energy barrier for NRR. Furthermore, we explored B-exposed and Ti-exposed surfaces to understand how different surfaces affect the reaction yield and efficiency and found that Ti-exposed surfaces with boron divacancy have the highest propensity for NRR. The maiden insights presented in this study on the role of transition metal-boron synergy and interfaces present significant additions to the fast-expanding knowledge on nanoscaled metal borides.

14.
Water Res ; 258: 121655, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38762914

RESUMO

Ammonia recovery from wastewater is of great significance for aquatic ecology safety, human health and carbon emissions reduction. Electrochemical methods have gained increasing attention since the authigenic base and acid of electrochemical systems can be used as stripper and absorbent for transmembrane chemisorption of ammonia, respectively. However, the separation of electrodes and gas permeable membrane (GPM) significantly restricts the ammonia transfer-transformation process and the authigenic acid-base utilization. To break the restrictions, this study developed a gas permeable membrane electrode assembly (GPMEA), which innovatively integrated anode and cathode on each side of GPM through easy phase inversion of polyvinylidene fluoride binder, respectively. With the GPMEA assembled in a stacked transmembrane electro-chemisorption (sTMECS) system, in situ utilization of authigenic acid and base for transmembrane electro-chemisorption of ammonia was achieved to enhance the ammonia recovery from wastewater. At current density of 60 A/m2, the transmembrane ammonia flux of the GPMEA was 693.0 ± 15.0 g N/(m2·d), which was 86 % and 28 % higher than those of separate GPM and membrane cathode, respectively. The specific energy consumption of the GPMEA was 9.7∼16.1 kWh/kg N, which were about 50 % and 25 % lower than that of separate GPM and membrane cathode, respectively. Moreover, the application of GPMEA in the ammonia recovery from wastewater is easy to scale up in the sTMECS system. Accordingly, with the features of excellent performance, energy saving and easy scale-up, the GPMEA showed good prospects in electrochemical ammonia recovery from wastewater.


Assuntos
Amônia , Eletrodos , Águas Residuárias , Amônia/química , Águas Residuárias/química , Membranas Artificiais , Eliminação de Resíduos Líquidos/métodos , Técnicas Eletroquímicas , Poluentes Químicos da Água/química
15.
ACS Appl Mater Interfaces ; 16(22): 28435-28440, 2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38768216

RESUMO

The optical and photonic characteristics of monolayer transition metal dichalcogenides (TMDs) play a pivotal role in their functionality as solar cell materials, light-emitting diodes (LEDs), and other electro-optical applications. In this study, we reveal the impact of prolonged illumination on the luminescence properties and Raman spectra of monolayered MoS2 and WS2─a process known as "light soaking". We find a light-induced transition from the physisorption to the chemisorption of ambient O2 and H2O molecules. In parallel, we observe the activation and passivation of defect sites in the samples (depending on their initial defect density), which is attributed to the adsorbed ambient molecules and the resulting light-driven interactions with defect sites. Thus, we can control the active defect density of monolayered TMDs and shed light on the fundamental mechanisms underlying their luminescence properties. Therefore, this work clarifies the source of changes to the luminescence properties of TMDs and opens the path toward their integration into advanced applications that may be affected by light soaking, such as solar cells and energy devices.

16.
ACS Nano ; 18(22): 14640-14649, 2024 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-38761149

RESUMO

The control of reaction selectivity is of great interest in chemistry and depends crucially on the revelation of key influencing factors. Based on well-defined molecule-substrate model systems, various influencing factors have been elucidated, focusing primarily on the molecular precursors and the underlying substrates themselves, while interfacial properties have recently been shown to be essential as well. However, the influence of molecular chemisorption direction on reaction selectivity, as a subtle interplay between molecules and underlying substrates, remains elusive. In this work, by a combination of scanning tunneling microscopy imaging and density functional theory calculations, we report the influence of molecular chemisorption direction on the reaction selectivity of two types of dehalogenative coupling on Au(111), i.e., polymerization and cyclization, at the atomic level. The diffusion step of a reactive dehalogenated intermediate in two different chemisorption directions was theoretically revealed to be the key to determining the corresponding reaction selectivity. Our results highlight the important role of molecular chemisorption directions in regulating the on-surface dehalogenative coupling reaction pathways and products, which provides fundamental insights into the control of reaction selectivity by exploiting some subtle interfacial parameters in on-surface reactions for the fabrication of target low-dimensional carbon nanostructures.

17.
Environ Sci Pollut Res Int ; 31(20): 29132-29147, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38568311

RESUMO

Layered double hydroxides (LDH) hold great promise as phosphate adsorbents; however, the conventional binary LDH exhibits low adsorption rate and adsorption capacity. In this study, Mg and La were chosen as binary metals in the synthesis of Mg-La LDH to enhance phosphate efficient adsorption. Different molar ratios of Mg to La (2:1, 3:1, and 4:1) were investigated to further enhance P adsorption. The best performing Mg-La LDH, with Mg to La ratio is 4:1 (LDH-4), presented a larger adsorption capacity and faster adsorption rate than other Mg-La LDH. The maximum adsorption capacity (87.23 mg/g) and the rapid adsorption rate in the initial 25 min of LDH-4 (70 mg/(g·h)) were at least 1.6 times and 1.8 times higher than the others. The kinetics, isotherms, the effect of initial pH and co-existing anions, and the adsorption-desorption cycle experiment were studied. The batch experiment results proved that the chemisorption progress occurred on the single-layered LDH surface and the optimized LDH exhibited strong anti-interference capability. Furthermore, the structural characteristics and adsorption mechanism were further investigated by SEM, BET, FTIR, XRD, and XPS. The characterization results showed that the different metal ratios could lead to changes in the metal hydroxide layer and the main ions inside. At lower Mg/La ratios, distortion occurred in the hydroxide layer, resulting in lower crystallinity and lower performance. The characterization results also proved that the main mechanisms of phosphate adsorption are electrostatic adsorption, ion exchange, and inner-sphere complexation. The results emphasized that the Mg-La LDH was efficient in phosphate removal and could be successfully used for this purpose.


Assuntos
Hidróxidos , Magnésio , Fosfatos , Adsorção , Hidróxidos/química , Fosfatos/química , Magnésio/química , Cinética , Lantânio/química , Poluentes Químicos da Água/química , Concentração de Íons de Hidrogênio
18.
Environ Sci Pollut Res Int ; 31(22): 32935-32949, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38671264

RESUMO

The high cost and low adsorption capacity of primary metal-organic frameworks (ZIF-8) limit their application in heavy metal removal. In this paper, Co/Zn bimetallic MOF materials were synthesized with excellent adsorption performance for As5+. The adsorption reached equilibrium after 180 min and the maximum adsorption was 250.088 mg/g. In addition, Co-ZIF-8 showed strong selective adsorption of As5+. The adsorption process model of Co-ZIF-8 fits well with the pseudo-second-order kinetic model (R2=0.997) and Langmuir isotherm model (R2=0.994), and it is demonstrated that the adsorption behavior of the adsorbent is a single layer of chemical adsorption. In addition, when the adsorbent enters the arsenic-containing solution, the surface of Co-ZIF-8 is hydrolyzed to produce a large number of Co-OH active sites, and As5+ arrives at the surface of Co-ZIF-8 by electrostatic adsorption and combines with the active sites to generate the arsenic-containing complex As-O-Co. After four cycles, Co-ZIF-8 showed 80% adsorption of As5+. This study not only provides a new method to capture As5+ in water by preparing MOF with partial replacement of the central metal, but also has great significance for the harmless disposal of polluted water.


Assuntos
Arsênio , Cobalto , Estruturas Metalorgânicas , Águas Residuárias , Poluentes Químicos da Água , Adsorção , Arsênio/química , Cobalto/química , Águas Residuárias/química , Poluentes Químicos da Água/química , Estruturas Metalorgânicas/química , Cinética , Purificação da Água/métodos
19.
Adv Sci (Weinh) ; 11(18): e2401868, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38460160

RESUMO

Metal-organic frameworks (MOFs) are promising candidates for room-temperature hydrogen storage materials after modification, thanks to their ability to chemisorb hydrogen. However, the hydrogen adsorption strength of these modified MOFs remains insufficient to meet the capacity and safety requirements of hydrogen storage systems. To address this challenge, a highly defective framework material known as de-MgMOF is prepared by gently annealing Mg-MOF-74. This material retains some of the crystal properties of the original Mg-MOF-74 and exhibits exceptional hydrogen storage capacity at above-ambient temperatures. The MgO5 knots around linker vacancies in de-MgMOF can adsorb a significant amount of dissociated and nondissociated hydrogen, with adsorption enthalpies ranging from -22.7 to -43.6 kJ mol-1, indicating a strong chemisorption interaction. By leveraging a spillover catalyst of Pt, the material achieves a reversible hydrogen storage capacity of 2.55 wt.% at 160 °C and 81 bar. Additionally, this material offers rapid hydrogen uptake/release, stable cycling, and convenient storage capabilities. A comprehensive techno-economic analysis demonstrates that this material outperforms many other hydrogen storage materials at the system level for on-board applications.

20.
ACS Appl Mater Interfaces ; 16(12): 15487-15495, 2024 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-38470979

RESUMO

Molybdenum disulfide (MoS2) quantum sheets (QSs) are attractive for applications due to their tunable energy band structures and optical and electronic properties. The photoluminescence quantum yield (PLQY) of MoS2 QSs achieved by mechanical and liquid exfoliation and chemical vapor deposition is low. Some studies have reported that chemical treatment and elemental doping can improve the PLQY of transition metal dichalcogenides (TMDs), but this is limited by complex instruments and reactions. In this study, a heat treatment method based on a polar solvent is reported to improve the PLQY and photoluminescence (PL) intensity of MoS2 QSs at room temperature. The absolute PLQY of treated MoS2 QSs is increased to 18.5%, and the PL intensity is increased by a factor of 64. This method is also effective for tungsten disulfide (WS2) QSs. The PL enhancement of QSs is attributed to oxidation of the edges. Such passivation/deformation of MoS2 QSs facilitates the radiative route rather than the nonradiative route, resulting in extreme enhancement of the PL. Our work could provide novel insights/routes toward the PL enhancement of TMD QSs.

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