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1.
Small ; : e2406701, 2024 Sep 23.
Artículo en Inglés | MEDLINE | ID: mdl-39308274

RESUMEN

The development of electrically conductive membranes is essential for advancing future technologies like electronic devices, supercapacitors, and batteries. Newly synthesized doubly interpenetrated 3D-Cd-MOF (Metal-Organic-Framework) containing angular tetra-carboxylate is found to display very poor electrical conductivity (10-11 S cm-1). However, it exhibits an exceptional ability to adsorb I2 (I2@Cd-MOF) which shows increased electrical conductivity of the order of 10-8 S cm-1. Following these results, the Cd-MOF is integrated into the PVDF-PVP (Polyvinylidene fluoride-Polyvinylpyrrolidone) polymeric mixed matrix membrane (MMM) and explores their I2 adsorption capabilities and electrical conductivities before and after I2 adsorption. Four polymeric MMMs with the loading of Cd-MOF 0, 20, 40, and 50% are tested for their I2 adsorption ability and their respective electrical conductivities. The 50% Cd-MOF-loaded MMM is found to exhibit higher adsorption of I2 (685 mg g-1) and significant enhancement in conductivity from 10-11 to 10-4 S cm-1. The raise in the electrical conductivity by 10 million times is attributed to the synergistic interactions between I2, Cd-MOF, PVDF, and PVP polymers as well as the increase in the concentration of charge carriers (holes) within the frameworks. This work serves as blueprint for controlling charge transfer in MMM to tune their electrical conductivity which opens a large window for advanced device applications.

2.
Chemosphere ; 365: 143312, 2024 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-39265732

RESUMEN

Global warming has been mainly attributed to the excessive release of carbon dioxide (CO2) to the atmosphere. Several CO2 capture and conversion technologies have been developed in the past few decades with their own merits and limitations. Electrochemical conversion of CO2 is one of the most attractive techniques for combating CO2 emissions. However, the efficacy of the electrochemical reduction of CO2 hinges on the efficiency of the utilized materials (i.e., electrocatalysts). Metal organic frameworks (MOFs)-based materials have recently emerged as attractive tools for various applications, including the electrochemical conversion of CO2. Although there are some review articles on CO2 capture and conversion using different materials, reviews focusing specifically on the electrochemical conversion of CO2 using MOFs-based materials are still comparatively lacking. Additionally, the field of electrochemical conversion of CO2 into valuable chemicals is currently gaining high momentum, requiring comprehensive and recent reviews, which would provide researchers/professionals with a quick and easy access to the recent developments in this rapidly evolving research area. Accordingly, this article comprehensively reviews recent studies on the electrochemical conversion of CO2 using pristine/modified/functionalized MOFs as well as composite materials containing MOFs. Additionally, single atom catalysts (SACs) derived from MOFs and their applications for the electrochemical conversion of CO2 has also been reviewed. Furthermore, obstacles, challenges, limitations, and remaining research gaps have been identified, and future works to tackle them have been highlighted. Overall, this review article provides valuable discussion and insights into the recent advancements in the field of electrochemical conversion of CO2 into chemicals using MOFs-based materials.

3.
ChemSusChem ; : e202401454, 2024 Sep 20.
Artículo en Inglés | MEDLINE | ID: mdl-39302821

RESUMEN

Two-dimensional (2D) conjugated metal-organic frameworks (c-MOFs) are promising materials for supercapacitor (SC) electrodes due to their high electrochemically accessible surface area coupled with superior electrical conductivity compared to traditional MOFs. Here, porous and non-porous HHB-Cu (HHB=hexahydroxybenzene), derived through surfactant-assisted synthesis, are studied as representative 2D c-MOF models, showing different reversible redox reactions with Na+ and Li+ in aqueous and organic electrolytes, respectively. We deployed these redox activities to design negative electrodes for hybrid SCs (HSCs), combining the battery-like property of HHB-Cu as negative electrode and the high capacitance and robust cyclic stability of activated carbon (AC) as positive electrode. In organic electrolyte, porous HHB-Cu-based HSC achieves a maximum cell specific capacity (Cs) of 22.1 mAhg-1 at 0.1 Ag-1, specific energy (Es) of 15.55 Whkg-1 at specific power (Ps) of 70.49 Wkg-1, and 77% cyclic stability after 3000 gravimetric charge-discharge (GCD) cycles at 1 Ag-1 (calculated on the mass of both electrode materials). In the aqueous electrolyte, porous HHB-Cu-based HSC displays a Cs of 13.9 mAhg-1 at 0.1 Ag-1, Es of 6.13 Whkg-1 at 44.05 Wkg-1, and 72.3% Cs retention after 3000 GCD cycles. The non-porous sample shows lower Es performance but better rate capability compared to the porous one.

4.
ACS Appl Bio Mater ; 7(9): 6201-6212, 2024 Sep 16.
Artículo en Inglés | MEDLINE | ID: mdl-39231419

RESUMEN

The synthesis of bioinspired metal-organic frameworks (MOFs) performed in mild conditions with a high quality is greatly demanded. Moreover, the influence of the morphology and structure of bio-MOFs on the cell interaction and toxicity is important to determine. In this work, we developed an ultrasound (US)-assisted synthesis of HKUST-1 MOFs under mild conditions and investigated the influence of the parameters of synthesis on the morphology, structure, and biological properties of the developed MOFs. It was found that the US power, reaction time, temperature, and type of solvent composition would affect the morphology, size, and yield of the obtained crystals. Employing the optimal synthetic conditions, five types of HKUST-1 MOFs were prepared, achieving highest yields (67.8-96.2%) and different morphologies (octahedral, dodecahedral, icosahedral). The relationship between the morphological features and biological properties of developed bio-MOFs was evaluated and discussed. The cellular association and cytotoxicity of MOF@US and MOF@US-PARG were studied on various cell cultures, i.e. normal mouse embryonic fibroblasts (MEF NF2), chronic myeloid leukemia (K562), and mouse melanoma (B16-F10). The experimental results showed that MOF@US-PARG has a higher percentage of association compared to MOF@US. It has also been shown that the cytotoxicity depends on the concentration and surface modification of the developed MOFs.


Asunto(s)
Materiales Biocompatibles , Ensayo de Materiales , Estructuras Metalorgánicas , Tamaño de la Partícula , Ratones , Animales , Estructuras Metalorgánicas/química , Estructuras Metalorgánicas/farmacología , Estructuras Metalorgánicas/síntesis química , Materiales Biocompatibles/química , Materiales Biocompatibles/farmacología , Materiales Biocompatibles/síntesis química , Humanos , Supervivencia Celular/efectos de los fármacos , Ondas Ultrasónicas , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/síntesis química , Propiedades de Superficie , Proliferación Celular/efectos de los fármacos , Línea Celular Tumoral
5.
Heliyon ; 10(17): e36540, 2024 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-39263092

RESUMEN

This study introduces a high-performance Ce-Co MOFs/Ti3C2Tx nanocomposite, synthesized via hydrothermal methods, designed to advance supercapacitor technology. The integration of Ce-Co metal-organic frameworks (MOFs) with Ti3C2Tx (Mxene) yields a composite that exhibits superior electrochemical properties. Structural analyses, including X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM), confirm the successful formation of the composite, featuring well-defined rod-like Ce-Co MOFs and layered Ti3C2Tx sheets. Electrochemical evaluation highlights the exceptional performance of the Ce-Co MOFs/Ti3C2Tx nanocomposite, achieving a specific capacitance of 483.3 Fg⁻1 at 10 mVs⁻1, a notable enhancement over the 200 Fg⁻1 of Ce-Co MOFs. It also delivers a high energy density of 78.48 Whkg⁻1 compared to 19 Whkg⁻1 for Ce-Co MOFs. Remarkably, the nanocomposite shows outstanding cyclic stability with a capacitance retention of 109 % after 4000 cycles and electrochemical surface area (ECSA) of 845 cm2, coupled with a reduced charge transfer resistance (Rct) of 2.601 Ω and an equivalent series resistance (ESR) of 0.8 Ω. These findings demonstrate that the Ce-Co MOFs/Ti3C2Tx nanocomposite is a groundbreaking material, offering enhanced energy storage, conductivity, and durability, positioning it as a leading candidate for next-generation supercapacitors.

6.
Se Pu ; 42(9): 819-826, 2024 Sep.
Artículo en Chino | MEDLINE | ID: mdl-39198941

RESUMEN

Red tides are a type of natural marine disaster caused by harmful algae characterized by a high toxicity, wide distribution, and long duration. Since the concentration of algal toxins in seawater increases with the occurrence of red tides, algal toxins detected in seawater could be used to predict the occurrence and evolution of red tides. Brevetoxin-A (BTX-A) is a secondary metabolite produced by the harmful algae Karenia brevis, whose detection in seawater could form the basis of an accurate warning system for incoming red tides. However, due to the inherent complexity of the seawater matrix and the extremely low levels of BTX-A in seawater, the use of instruments for its direct detection is difficult. Therefore, there is an urgent need to develop a sample pretreatment method for the efficient enrichment of BTX-A in seawater. In this study, a metal-organic backbone material (UiO-66) and its composite with silica microspheres (SiO2@UiO-66) were successfully synthesized using the solvothermal method. The prepared SiO2@UiO-66 exhibited good hydrophilicity, water stability, and large specific surface area. Furthermore, it also exhibited hydrogen bonding and electrostatic interactions with BTX-A, had a strong affinity for BTX-A, and was able to efficiently adsorb BTX-A in complex matrices. Therefore, SiO2@UiO-66 showed potential as a novel packing material for the extraction of BTX-A from solid phase extraction columns. Combined with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), a highly sensitive detection method for the determination of BTX-A in marine water was established. The established analytical method had a low detection limit (3.0 pg/mL), a wide linear range (10.0 -200.0 pg/mL), and a good linear relationship (R=0.9992). Combined with the Fujian Province Red Tide Monitoring and Early Warning Information 2021 issued by the Fujian Provincial Oceanic and Fisheries Bureau, the analytical method established herein was successfully applied to analyze and monitor the content of BTX-A in actual seawater samples. This highlights the proposed system's potential for use as an early warning factor in the monitoring of red tides, representing a simple and fast pretreatment methodology for the detection of BTX-A in seawater.


Asunto(s)
Toxinas Marinas , Estructuras Metalorgánicas , Oxocinas , Agua de Mar , Extracción en Fase Sólida , Circonio , Agua de Mar/química , Oxocinas/análisis , Oxocinas/química , Estructuras Metalorgánicas/química , Circonio/química , Contaminantes Químicos del Agua/análisis , Exotoxinas/análisis , Exotoxinas/química , Toxinas Poliéteres
7.
Molecules ; 29(15)2024 Aug 05.
Artículo en Inglés | MEDLINE | ID: mdl-39125117

RESUMEN

The solvothermal synthesis of LnCl3.nH2O with terephthalic acid (benzene-1,4-dicarboxylic acid, H2BDC) produced metal-organic frameworks (LnBDC), [Ln2(BDC)3(H2O)4]∞, where Ln = Sm, Eu, Tb, and Dy. The materials obtained were characterized by a number of physico-chemical techniques. The influence of the ionic radius of the lanthanides on the microstructural characteristics of the Ln-MOFs was evaluated by performing Rietveld refinement. The MOFs obtained were tested as fluorescent sensors for numerous cations and anions in water. The highly luminescent EuBDC and TbBDC demonstrated multi-responsive luminescence sensing functions to detect Ag(I), Fe(III), Cr(III), and Cr(VI), which are essential for their environmental applications. By applying the non-linear Stern-Volmer equation, the fluorescent quenching mechanism was determined. The stability of the obtained materials in water in a wide pH range (acidity pH = 4 and alkalinity pH = 9 solutions) was confirmed.

8.
Sci Rep ; 14(1): 18144, 2024 08 05.
Artículo en Inglés | MEDLINE | ID: mdl-39103470

RESUMEN

The exclusion mechanism of food contaminants such as bisphenol A (BPA), Flavonoids (FLA), and Goitrin (GOI) onto the novel gallium-metal organic framework (MOF) and functionalized MOF with oxalamide group (MOF-OX) is evaluated by utilizing molecular dynamics (MD) and Metadynamics simulations. The atoms in molecules (AIM) analysis detected different types of atomic interactions between contaminant molecules and substrates. To assess this procedure, a range of descriptors including interaction energies, root mean square displacement, radial distribution function (RDF), density, hydrogen bond count (HB), and contact numbers are examined across the simulation trajectories. The most important elements in the stability of the systems under examination are found to be stacking π-π and HB interactions. It was confirmed by a significant value of total interaction energy for BPA/MOF-OX (- 338.21 kJ mol-1) and BPA/MOF (- 389.95 kJ mol-1) complexes. Evaluation of interaction energies reveals that L-J interaction plays an essential role in the adsorption of food contaminants on the substrates. The free energy values for the stability systems of BPA/MOF and BPA/MOF-OX complexes at their global minima reached about BPA/MOF = - 254.29 kJ mol-1 and BPA/MOF-OX = - 187.62 kJ mol-1, respectively. Nevertheless, this work provides a new strategy for the preparation of a new hierarchical tree-dimensional of the Ga-MOF hybrid material for the adsorption and exclusion of food contaminates and their effect on human health.


Asunto(s)
Contaminación de Alimentos , Galio , Estructuras Metalorgánicas , Simulación de Dinámica Molecular , Estructuras Metalorgánicas/química , Galio/química , Contaminación de Alimentos/análisis , Fenoles/química , Fenoles/análisis , Compuestos de Bencidrilo/química , Compuestos de Bencidrilo/análisis , Enlace de Hidrógeno , Adsorción , Flavonoides/química , Flavonoides/análisis
9.
Small ; : e2404438, 2024 Aug 05.
Artículo en Inglés | MEDLINE | ID: mdl-39101630

RESUMEN

Hematite (α-Fe2O3) has become a research hotspot in the field of photoelectrochemical water splitting (PEC-WS), but the low photogenerated carrier separation efficiency limits further application. The electronic structure regulation, such as element doping and organic functional groups with different electrical properties, is applied to alleviate the problems of poor electrical conductivity, interface defects, and band mismatch. Herein, α-Fe2O3 photoanodes are modified to regulate their electric structures and improve photogenerated carrier transport by the bimetallic metal-organic frameworks (MOFs), which are constructed with Fe/Ni and terephthalate (BDC) with 2-substitution of different organic functional groups (─H, ─Br, ─NO2 and ─NH2). The α-Fe2O3 photoanode loaded with FeNi-NH2BDC MOF catalyst exhibits the optimal photocurrent density (2 mA cm-2) at 1.23 VRHE, which is 2.33 times that of the pure α-Fe2O3 photoanode. The detailed PEC analyses demonstrate that the bimetallic synergistic effect between Fe and Ni can improve the conductivity and inhibit the photogenerated carrier recombination of α-Fe2O3 photoanodes. The ─NH2 group as an electron-donor group can effectively regulate the electron distribution and band structure of α-Fe2O3 photoanodes to prolong the lifetime of photogenerated holes, which facilitates photogenerated carrier transport and further enhances the PEC-WS performance of α-Fe2O3 photoanode.

10.
Talanta ; 280: 126766, 2024 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-39191106

RESUMEN

Glypican-1 (GPC-1) protein-positive small extracellular vesicles (GPC-1+-sEV) have been proposed as potential biomarkers for early diagnosis of pancreatic cancer. In this study, we present an integrated real-time isolation and detection platform (IRTIDP) to capture and analyze GPC-1+-sEV directly from sera of pancreatic cancer patients. First, CD63 antibody-modified metal-organic framework (MOF) materials were utilized to enrich sEVs with a capture efficiency of 93.93 %. Second, a SERS probe was constructed by Raman reporter 4-MBA and GPC-1 antibody modified SERS active silver nanoparticles (AgNPs), which formed a sandwich complex structure of "MOFs@GPC-1+-sEV@AgNPs-4-MBA" with MOFs-enriched sEVs. The IRTSDP can complete the capture and detection process within 35 min, with a detection limit for 1 GPC-1+-sEV/µL, and linear range between 105∼109 GPC-1+-sEV/mL. Furthermore, this approach has been applied to quantify serum sEV GPC-1 in clinical pancreatic cancer patients. Based on the SERS intensity analysis, pancreatic cancer patients can be distinguished from pancreatic cystadenoma patients and healthy individuals effectively using this innovative platform that provides highly specific and sensitive means for early diagnosis of pancreatic cancer as well as other tumor types.


Asunto(s)
Vesículas Extracelulares , Glipicanos , Nanopartículas del Metal , Neoplasias Pancreáticas , Humanos , Glipicanos/sangre , Glipicanos/inmunología , Neoplasias Pancreáticas/diagnóstico , Neoplasias Pancreáticas/sangre , Vesículas Extracelulares/química , Nanopartículas del Metal/química , Espectrometría Raman/métodos , Plata/química , Estructuras Metalorgánicas/química , Biomarcadores de Tumor/sangre , Biomarcadores de Tumor/análisis , Límite de Detección , Tetraspanina 30
11.
Int J Biol Macromol ; 277(Pt 3): 134296, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-39094888

RESUMEN

Anthocyanidins and anthocyanins are one subclass of flavonoids in plants with diverse biological functions and have health-promoting effects. Dihydroflavonol 4-reductase (DFR) is one of the important enzymes involved in the biosynthesis of anthocyanidins and other flavonoids. Here, a new MOF-based nano-immobilized DFR enzyme acting as a nano-biocatalyst for the production of anthocyanidins in vitro was designed. We prepared UiO-66-NH2 MOF nano-carrier and recombinant DFR enzyme from genetic engineering. DFR@UiO-66-NH2 nano-immobilized enzyme was constructed based on covalent bonding under the optimum immobilization conditions of the enzyme/carrier ratio of 250 mg/g, 37 °C, pH 6.5 and fixation time of 10 min. DFR@UiO-66-NH2 was characterized and its catalytic function for the synthesis of anthocyanidins in vitro was testified using UPLC-QQQ-MS analysis. Compared with free DFR enzyme, the enzymatic reaction catalyzed by DFR@UiO-66-NH2 was more easily for manipulation in a wide range of reaction temperatures and pH values. DFR@UiO-66-NH2 had better thermal stability, enhanced adaptability, longer-term storage, outstanding tolerances to the influences of several organic reagents and Zn2+, Cu2+ and Fe2+ ions, and relatively good reusability. This work developed a new MOF-based nano-immobilized biocatalyst that had a good prospect of application in the green synthesis of anthocyanins in the future.


Asunto(s)
Antocianinas , Biocatálisis , Enzimas Inmovilizadas , Estructuras Metalorgánicas , Antocianinas/química , Antocianinas/biosíntesis , Enzimas Inmovilizadas/química , Enzimas Inmovilizadas/metabolismo , Estructuras Metalorgánicas/química , Concentración de Iones de Hidrógeno , Oxidorreductasas de Alcohol/química , Oxidorreductasas de Alcohol/metabolismo , Oxidorreductasas de Alcohol/genética , Temperatura , Estabilidad de Enzimas
12.
Int J Biol Macromol ; 279(Pt 1): 135148, 2024 Aug 28.
Artículo en Inglés | MEDLINE | ID: mdl-39214202

RESUMEN

The accumulation of uremic toxins in the human body poses a deadly risk because it causes chronic kidney disease. To increase the effectiveness of hemodialysis and raise the survival rate, these toxins must be effectively removed from the bloodstream. Developing effective materials for removing these dangerous substances requires a thorough understanding of the interactions between an adsorbent and the uremic toxins. Thankfully, metal-organic frameworks (MOFs) have shown considerable promise for the identification and treatment of kidney disorders. Herein, cotton gauze fabrics (CGF) were carboxylated using monochloroacetic acid to produce carboxymethylated cotton gauze fabrics (CM-CGF). CM-CGF was subsequently decorated in situ with zeolitic imidazolate framework-67, resulting in carboxymethylated cotton gauze fabrics-zeolitic imidazolate framework-67 (CM-CGF-ZIF). The CGF, CM-CGF, and CM-CGF-ZIF were evaluated for potential kidney applications by removing uric acid and creatinine from mimic blood. The results showed that CM-CGF-ZIF had the highest adsorption of uric acid and creatinine. The maximum adsorption capacity of uric acid and creatinine was 164 and 222 mg/g for CM-CGF-ZIF, respectively, compared to 45 and 67 mg/g for CGF. CM-CGF-ZIF showed excellent antibacterial activity, good antifungal activity, low cytotoxicity, and a satisfactory level of blood compatibility.

13.
Sci Rep ; 14(1): 15434, 2024 Jul 04.
Artículo en Inglés | MEDLINE | ID: mdl-38965393

RESUMEN

In the paper, high specific surface area (SSA) mono and bimetallic zeolitic imidazolate frameworks (ZIFs) based on zinc and cobalt metals are successfully synthesized at room temperature using different ratios of Zn to Co salts as precursors and ammonium as a solvent to tailor the properties of the produced ZIF and optimize the efficiency of the particles in water treatment from dye and copper ions, simultaneously. The results declare that monometallic and bimetallic ZIF microparticles are formed using ammonium and the tuning of pore sizes and also increasing the SSA by inserting the Co ions in Zn-ZIF particles is accessible. It leads to a significant increase in the thermal stability of bimetallic Zn/Co-ZIF and the appearance of an absorption band in the visible region due to the existence of Co in the bimetallic structures. The bandgap energies of bimetallic ZIFs are close to that of the monometallic Co-ZIF-8, indicating controlling the bandgap by Co ZIF. Furthermore, the ZIFs samples are applied for water treatment from copper ions (10 and 184 ppm) and methylene blue (10 ppm) under visible irradiation and the optimized multifunctional bimetallic Zn/Co ZIF is introduced as an admirable candidate for water treatment even in acidic conditions.

14.
Adv Mater ; 36(33): e2401559, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38958107

RESUMEN

Label-free proteomics is widely used to identify disease mechanism and potential therapeutic targets. However, deep proteomics with ultratrace clinical specimen remains a major technical challenge due to extensive contact loss during complex sample pretreatment. Here, a hybrid of four boronic acid-rich lanthanide metal-organic frameworks (MOFs) with high protein affinity is introduced to capture proteins in ultratrace samples jointly by nitrogen-boronate complexation, cation-π and ionic interactions. A MOFs Aided Sample Preparation (MASP) workflow that shrinks sample volume and integrates lysis, protein capture, protein digestion and peptide collection steps into a single PCR tube to minimize sample loss caused by non-specific absorption, is proposed further. MASP is validated to quantify ≈1800 proteins in 10 HEK-293T cells. MASP is applied to profile cerebrospinal fluid (CSF) proteome from cerebral stroke and brain damaged patients, and identified ≈3700 proteins in 1 µL CSF. MASP is further demonstrated to detect ≈9600 proteins in as few as 50 µg mouse brain tissues. MASP thus enables deep, scalable, and reproducible proteome on precious clinical samples with low abundant proteins.


Asunto(s)
Ácidos Borónicos , Elementos de la Serie de los Lantanoides , Estructuras Metalorgánicas , Proteómica , Humanos , Estructuras Metalorgánicas/química , Proteómica/métodos , Animales , Ácidos Borónicos/química , Ratones , Elementos de la Serie de los Lantanoides/química , Células HEK293 , Proteoma/análisis , Encéfalo/metabolismo
15.
J Colloid Interface Sci ; 676: 884-895, 2024 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-39067223

RESUMEN

Developing high active and stable cost-effective bifunctional electrocatalysts for overall water splitting to produce hydrogen is of vital significance in clean and sustainable energy development. This work has prepared a novel porous unreported MOF (Ni-DPT) as a precursor to successfully synthesize a non-noble bifunctional NiCoP/Ni12P5@NF electrocatalyst through doping strategy and interface engineering. This catalyst is constructed by layered self-supporting arrays with heterojunction interface and rich nitrogen-phosphorus doping. Structural characterizations and the density function theory (DFT) calculations confirm that the interface effect of NiCoP/Ni12P5 heterojunction can regulate the electronic structure of the catalyst to optimize the Gibbs free energy of hydrogen (ΔGH*); simultaneously, the defect-rich layered nanoarrays can expose more active sites, shorten mass transfer distance, and generate a self-supporting structure for in-situ reinforcing the structural stability. As a result, this NiCoP/Ni12P5@NF catalyst exhibits favorable electrocatalytic performance, which simply needs overpotentials of 100 mV for HER and 310 mV for OER, respectively, at a current density of 10 mA·cm-2. The anion exchange membrane electrolyzer assembled with this NiCoP/Ni12P5@NF as both anode and cathode catalysts can operate stably for 200 h at a current density of 100 mA·cm-2 with an insignificant voltage decrease. This work may provide some inspiration for the further rational design of inexpensive non-noble multifunctional electrocatalysts and electrode materials for water splitting to generate hydrogen.

16.
Environ Res ; 258: 119404, 2024 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-38880323

RESUMEN

Adsorption is a promising way to remove persistent organic pollutants (POPs), a major environmental issue. With their high porosity and vast surface areas, MOFs are suited for POP removal due to their excellent adsorption capabilities. This review addresses the intricate principles of MOF-mediated adsorption and helps to future attempts to mitigate organic water pollution. This review examines the complicated concepts of MOF-mediated adsorption, including MOF synthesis methodologies, adsorption mechanisms, and material tunability and adaptability. MOFs' ability to adsorb POPs via electrostatic forces, acid-base interactions, hydrogen bonds, and pi-pi interactions is elaborated. This review demonstrates its versatility in eliminating many types of contaminants. Functionalizing, adding metal nanoparticles, or changing MOFs after they are created can improve their performance and remove contaminants. This paper also discusses MOF-based pollutant removal issues and future prospects, including adsorption capacity, selectivity, scale-up for practical application, stability, and recovery. These obstacles can be overcome by rationally designing MOFs, developing composite materials, and improving material production and characterization. Overall, MOF technology research and innovation hold considerable promise for environmental pollution solutions and sustainable remediation. Desorption and regeneration in MOFs are also included in the review, along with methods for improving pollutant removal efficiency and sustainability. Case studies of effective MOF regeneration and scaling up for practical deployment are discussed, along with future ideas for addressing these hurdles.


Asunto(s)
Estructuras Metalorgánicas , Contaminantes Orgánicos Persistentes , Adsorción , Estructuras Metalorgánicas/química , Contaminantes Orgánicos Persistentes/química , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/análisis
17.
Chemistry ; 30(47): e202401644, 2024 Aug 22.
Artículo en Inglés | MEDLINE | ID: mdl-38869378

RESUMEN

Herein, a series of monometallic Ni-, Co- and Zn-MOFs and bimetallic NiCo-, NiZn- and CoZn-MOFs of formula M2(BDC)2DABCO and (M,M')2(BDC)2DABCO, respectively, (M, M'=metal) with the same pillar and layer linkers 1,4-diazabicyclo[2.2.2]octane (DABCO) and benzene-1,4-dicarboxylate (BDC) were prepared through a fast microwave-assisted thermal conversion synthesis method (MW) within only 12 min. In the bimetallic MOFs the ratio M:M' was 4 : 1. The mono- and bimetallic MOFs were selected to systematically explore the catalytic-activity of their derived metal oxide/hydroxides for the oxygen evolution reaction (OER). Among all tested bimetallic MOF-derived catalysts, the NiCoMOF exhibits superior catalytic activity for the OER with the lowest overpotentials of 301 mV and Tafel slopes of 42 mV dec-1 on a rotating disk glassy carbon electrode (RD-GCE) in 1 mol L-1 KOH electrolyte at a current density of 10 mA cm-2. In addition, NiCoMOF was insitu grown in just 25 min by the MW synthesis on the surface of nickel foam (NF) with, for example, a mass loading of 16.6 mgMOF/gNF, where overpotentials of 313 and 328 mV at current densities of 50 and 300 mA cm-2, respectively, were delivered and superior long-term stability for practical OER application. The low Tafel slope of 27 mV dec-1, as well as a low reaction resistance from electrochemical impedance spectroscopy (EIS) measurement (Rfar=2 Ω), confirm the excellent OER performance of this NiCoMOF/NF composite. During the electrocatalytic processes or even before upon KOH pre-treatment, the MOFs are transformed to the mixed-metal hydroxide phase α-/ß-M(OH)2 which presents the active species in the reactions (turnover frequency TOF=0.252 s-1 at an overpotential of 320 mV). Compared to the TOF from ß-M(OH)2 (0.002 s-1), our study demonstrates that a bimetallic MOF improves the electrocatalytic performance of the derived catalyst by giving an intimate and uniform mixture of the involved metals at the nanoscale.

18.
Adv Mater ; : e2404384, 2024 Jun 29.
Artículo en Inglés | MEDLINE | ID: mdl-38943469

RESUMEN

Films and patterns of 3D-oriented metal-organic frameworks (MOFs) afford well-ordered pore structures extending across centimeter-scale areas. These macroscopic domains of aligned pores are pivotal to enhance diffusion along specific pathways and orient functional guests. The anisotropic properties emerging from this alignment are beneficial for applications in ion conductivity and photonics. However, the structure of 3D-oriented MOF films and patterns can rapidly degrade under humid and acidic conditions. Thus, more durable 3D-ordered porous systems are desired for practical applications. Here, oriented porous polymer films and patterns are prepared by using heteroepitaxially oriented N3-functionalized MOF films as precursor materials. The film fabrication protocol utilizes an azide-alkyne cycloaddition on the Cu2(AzBPDC)2DABCO MOF. The micropatterning protocol exploits the X-ray sensitivity of azide groups in Cu2(AzBPDC)2DABCO, enabling selective degradation in the irradiated areas. The masked regions of the MOF film retain their N3-functionality, allowing for subsequent cross-linking through azide-alkyne coupling. Subsequent acidic treatment removes the Cu ions from the MOF, yielding porous polymer micro-patterns. The polymer has high chemical stability and shows an anisotropic fluorescent response. The use of 3D-oriented MOF systems as precursors for the fabrication of oriented porous polymers will facilitate the progress of optical components for photonic applications.

19.
Se Pu ; 42(6): 524-532, 2024 Jun.
Artículo en Chino | MEDLINE | ID: mdl-38845513

RESUMEN

The stationary phase is the heart of chromatographic separation technology and a critical contributor to the overall separation performance of a chromatographic separation technique. However, traditional silicon-based materials designed for this purpose usually feature complex preparation processes, suboptimal permeability, pronounced mass-transfer resistance, and limited pH-range compatibility. These limitations have spurred ongoing research efforts aimed at developing new chromatographic stationary phases characterized by higher separation efficiency, adaptable selectivity, and a broader scope of applicability. In this context, the scientific community has made significant strides toward the development of new-generation materials suitable for use as chromatographic stationary phases. These materials include carbon-based nanomaterial arrays, carbon quantum dots, and two-dimensional (2D) materials. 2D-materials are characterized by nanometer-scale thicknesses, extensive specific surface areas, distinctive layered structures, and outstanding mechanical properties under standard conditions. Thus, these materials demonstrate excellent utility in various applications, such as electrical and thermal conductivity enhancements, gas storage and separation solutions, membrane separation technologies, and catalysis. Graphene, which is arguably the most popular 2D-material used for chromatographic separation, consists of a 2D-lattice of carbon atoms arranged in a single layer, with a large specific surface area and efficient adsorption properties. Its widespread adoption in research and various industries is a testament to its versatility and effectiveness. In addition to graphene, the scientific community has developed various 2D-materials that mirror the layered structures of graphene, such as boron nitride, transition-metal sulfides, and 2D porous organic frameworks, all of which offer unique advantages. 2D porous organic frameworks, in particular, have received attention because of their nanosheet morphology, one-dimensional pores, and special interlayer forces; thus, these frameworks are considered promising candidate chromatographic stationary phase materials. Such recognition is especially true for 2D-metal organic frameworks (MOFs) and 2D-covalent organic frameworks (COFs), which exhibit low densities, high porosities, and substantial specific surface areas. The modifiability of these materials, in terms of pore size, shape, functional groups, and layer-stacking arrangements allows for excellent separation selectivity, highlighting their promising potential in chromatographic separation. Compared with their three-dimensional counterparts, 2D-MOFs feature a simple pore structure that offers reduced mass-transfer resistance and enhanced column efficiency. These attributes highlight the advantages of 2D-MOF nanosheets as chromatographic stationary phases. Similarly, 2D-COFs, given their high specific surface area and porosity, not only exhibit great thermal stability and chemical tolerance but also support a wide selection of solvents and operational conditions. Therefore, their role in the preparation of chromatographic stationary phases is considered highly promising. This review discusses the latest research developments in 2D porous organic framework materials in the context of gas- and liquid-chromatographic stationary phases. It introduces the synthesis methods for these novel materials, elucidates their retention mechanisms, and describes the applications of other 2D-materials, such as graphene, its derivatives, graphitic carbon nitride, and boron nitride, in chromatography. This review aims to shed light on the promising development prospects and future directions of 2D-materials in the field of chromatographic separation, offering valuable insights into the rational design and application of new 2D-materials in chromatography.

20.
Sci Rep ; 14(1): 14101, 2024 Jun 19.
Artículo en Inglés | MEDLINE | ID: mdl-38890358

RESUMEN

The strategy of designing heterogeneous porous catalysts by a post-modification method is a smart strategy to increase the catalytic power of desired catalysts. Accordingly, in this report, metal-organic frameworks based on titanium with acetic acid pending were designed and synthesized via post-modification method. The structure of the target catalyst has been investigated using different techniques such as FT-IR, XRD, SEM, EDX, Mapping, and N2 adsorption/desorption (BET/the BJH) the correctness of its formation has been proven. The catalytic application of Ti-based MOFs functionalized with acetic acid was evaluated in the preparation of new spiropyrans, and the obtained results show that the catalytic performance is improved by this modification. The strategy of designing heterogeneous porous catalysts through post-modification methods presents a sophisticated approach to enhancing the catalytic efficacy of desired catalysts. In this context, our study focuses on the synthesis and characterization of metal-organic frameworks (MOFs) based on titanium, functionalized with acetic acid pendants, using a post-modification method. Various characterization techniques, including Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), mapping, and N2 adsorption/desorption (BET/BJH), were employed to investigate the structure and composition of the synthesized catalyst. These techniques collectively confirmed the successful formation and structural integrity of the target catalyst. The structure of the synthesized products was confirmed by melting point, 1H-NMR and 13C-NMR and FT-IR techniques. Examining the general process of catalyst synthesis and its catalytic application shows that the mentioned modification is very useful for catalytic purposes. The presented catalyst was used in synthesis of a wide range of biologically active spiropyrans with good yields. The simultaneous presence of several biologically active cores in the synthesized products will highlight the biological properties of these compounds. The present study offers a promising insight into the rational design, synthesis, and application of task-specific porous catalysts, particularly in the context of synthesizing biologically active candidate molecules.

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