Facile synthesis of porphyrin-MOFs with high photo-Fenton activity to efficiently degrade ciprofloxacin.
Journal of colloid and interface science
The slow conversion of Fe(Ⅱ)/Fe(III) cycle was largely limited the degradation efficiency of many photo-Fenton systems. Herein, four Fe-MOFs nanorods (namely Fe-TCPP-1, Fe-TCPP-2, Fe-TCPP-3, Fe-TCPP-4) with decreasing length-diameter ratios were synthesized in a household microwave oven, using photosensitizer porphyrin and iron ions with Fenton activity as building blocks. Among them, the Fe-TCPP-3 exhibited high photogenerated electron-hole (e-h) separation efficiency and largest pore structure, endowing Fe-TCPP-3 with superior photo-Fenton property. In addition, Fe-TCPP-3 based photo-Fenton system was applied to efficiently degrade antibiotic ciprofloxacin (CIP) under neutral condition, due to the continuously generated reactive species (h, e, OH, O, O) in Fe-TCPP-3 under visible-light irradiation. With irradiation for 30 min, the degradation efficiency of the system could reach about 73 %, which was about 26-fold towards the system without light irradiation. This study paved a way to modulating the photo-Fenton activity of MOF-based catalysts.
10.1016/j.jcis.2022.04.104
Photothermal-boosted effect of binary CuFe bimetallic magnetic MOF heterojunction for high-performance photo-Fenton degradation of organic pollutants.
Shi Shuo,Han Ximei,Liu Jie,Lan Xi,Feng Jianxing,Li Yuchen,Zhang Wentao,Wang Jianlong
The Science of the total environment
Overcoming the relatively low catalytic activity and strict acid pH condition of common photo-Fenton reaction is the key to alleviate the serious global burden caused by common organic pollutants. Herein, a binary homologous bimetallic heterojunction of magnetic CuFeO@MIL-100(Fe, Cu) metal-organic frameworks (MCuFe MOF) with photothermal-boosted photo-Fenton activity is constructed as an ideal practical photo-Fenton catalyst for the degradation of organic pollutants. Through an in-situ derivation strategy, the formed homologous bimetallic heterojunction with binary redox couples can simultaneously improve the visible light harvesting capacity and expedite the separation and transfer of photogenerated electrons/holes pairs, leading to the continuous and rapid circulation of both Fe/Fe and Cu/Cu redox couples. Notably, the heterojunction shows intrinsic photo-thermal conversion effect, which is found to be beneficial to boost the photo-Fenton activity. Impressively, MCuFe MOF shows remarkable catalytic performance towards the degradation of various organic pollutants by comprehensively increasing HO decomposition efficiency and decreasing the required dosage of MCuFe MOF (0.05 g L) with a wide pH range (3.0-10.0). As such, a photo-Fenton catalyst consisting of binary homologous bimetallic heterojunction is first disclosed, as well as its photothermal-enhanced effect, which is expected to drive great advance in the degradation of organic pollutants for practical applications.
10.1016/j.scitotenv.2021.148883
Adsorption and fenton-like oxidation of ofloxacin in wastewater using hybrid MOF bimetallic Fe/Ni nanoparticles.
Chemosphere
Since ofloxacin (OFX) is one of many common antibiotics, which effluxes into aquatic environment in relatively high concentration, it has become of significant environmental concern due to the potential for increased antibiotic resistance. In this study, an innovative functional Fe/Ni@ZIF-8 composite was successfully used for the Fenton-like oxidation of OFX, with a OFX removal efficiency >98% under optimal conditions. FTIR analysis confirmed that OFX removal occurred via adsorption to Fe/Ni@ZIF-8 by a combination of π-π bond intercalation and electrostatic interaction, while XPS revealed that the Fe/Ni NPs in Fe/Ni@ZIF-8 were also involved in oxidation. Furthermore, LC-MS analysis identified the presence of several OFX degradation products post exposure, which indicted that Fe/Ni NPs in Fe/Ni@ZIF-8 reacted with HO to form •OH, leading to Fenton-like oxidation of OFX. Thus overall, OFX removal by Fe/Ni@ZIF-8 involved both adsorption to ZIF-8 and Fenton-like oxidation by Fe/Ni NPs. A synergistic mechanism for OFX removal by Fe/Ni@ZIF-8 was thus proposed. The removal efficiency of the synthesized catalysts remained high (above 65%) even after a 5th reuse cycle, which reflected the high stability of Fe/Ni@ZIF-8. Overall, this study demonstrated that Fe/Ni@ZIF-8 had significant potential for the removal of OFX from wastewaters with a removal efficiency >90%.
10.1016/j.chemosphere.2022.135936
Construction of MOF/COF Hybrids for Boosting Sunlight-Induced Fenton-like Photocatalytic Removal of Organic Pollutants.
Guo Xiandi,Yin Dongguang,Khaing Kyu Kyu,Wang Jun,Luo Zhaoyue,Zhang Yong
Inorganic chemistry
In this work, a metal-organic framework (MOF) material of NH-MIL88B was hybridized with TpPa-1-COF through covalent bonding, and the hybrid was subsequently employed for the degradation of Rhodamine B (RhB) and tetracycline (TC) by simulated sunlight-induced Fenton-like exciting HO. The obtained results show that its photocatalytic activity is much better than those of its parent MOF and covalent organic framework (COF). Moreover, it is much higher than that of bare photocatalysis without Fenton-like excitation of HO. The high degradation efficiency is ascribed to two factors. One is the formation of hybrid, which promotes charge separation and light absorbance. Another is the Fenton-like excitation of HO, which produces more hydroxyl radicals (OH). This report presents a facile approach to greatly improve the photocatalytic property of MOF materials by the formation of hybrid with COFs and Fenton-like excitation of HO.
10.1021/acs.inorgchem.1c02198
Enhanced Fenton-like catalysis for pollutants removal via MOF-derived CoFeO membrane: Oxygen vacancy-mediated mechanism.
Chemosphere
Traditional batch configuration is not sustainable due to catalyst leaching and ineffective recovery. Herein, a novel membrane-based catalyst with oxygen vacancies is developed, which assembled metal-organic-framework cobalt ferrite nanocrystals (MOF-d CoFeO) on polyvinylidene fluoride membrane to activate peroxymonosulfate (PMS) for catalytic degradation of emerging pollutants. MOF-d CoFeO are synthesized by one-step pyrolysis using Co/Fe bimetallic organic frameworks (CoFe bi-MOF) with tunable cobalt content as a template (x/3-x represented the molar ratio of Co and Fe in MOF). Intriguingly, MOF-d CoFeO membrane exhibits excellent PMS activation efficiency as indicated by 95.12% removal of the probe chemical (bisphenol A) at 0.5 mM PMS (∼100 L m h at the loading of 10 mg), which is significantly higher than the traditional CoFeO suspension system (34.16%). Experimental results show that the membrane has excellent anti-interference ability to anions and dissolved organic matter, and can effectively degrade a variety of emerging pollutants, and its performance is not inhibited by the change of solution pH (3-9) or the long-term (20 h) continuous flow operation. EPR and quenching experiments show that catalytic degradation is the result of the synergistic effect of radicals and non-radicals. The oxygen vacancy-mediated mechanism can explain the formation of active substances, and the formation of O plays an important role in the degradation of bisphenol A. This study provides a membrane-based strategy for effective and sustainable removal of emerging pollutants.
10.1016/j.chemosphere.2022.135301
Efficient photocatalytic degradation of rhodamine 6G with a quantum dot-metal organic framework nanocomposite.
Kaur Rajnish,Vellingiri Kowsalya,Kim Ki-Hyun,Paul A K,Deep Akash
Chemosphere
The hybrid structures of metal organic frameworks (MOFs) and nanoparticles may offer the realization of effective photocatalytic materials due to combined benefits of the porous and molecular sieving properties of MOF matrix and the functional characteristics of encapsulated nanoparticles. In this study, cadmium telluride (CdTe) quantum dots (QD) are conjugated with a europium-MOF for the synthesis of a novel nanocomposite material with photocatalytic properties. Successful synthesis of a QD/Eu-MOF nanocomposite was characterized with various spectroscopic and microscopic techniques. This QD/Eu-MOF is found to be an effective catalyst to complete the degradation of Rhodamine 6G dye within 50 min.
10.1016/j.chemosphere.2016.04.024
Activation of peroxymonosulfate by CoFeO loaded on metal-organic framework for the degradation of organic dye.
Zhang Ke,Sun Dedong,Ma Chun,Wang Guanlong,Dong Xiaoli,Zhang Xinxin
Chemosphere
The magnetic composite CoFeO/ZIF-8 based on metal organic framework (MOF) with high specific surface area and high activity was synthesized by solvothermal method. The prepared catalysts were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), vibration sample magnetometer (VSM) and N adsorption-desorption isotherms, respectively. After characterization, CoFeO/ZIF-8 was applied to heterogeneous activation of peroxymonosulfate (PMS) for degrading methylene blue (MB). The result showed that the 0.075-CoFeO/ZIF-8 sample had the excellent catalytic activity. After catalytic reaction for 60 min, the degradation efficiency of MB (20 mg/L) reached about 97.9% at room temperature of 20 °C. The quenching experiment and electron paramagnetic resonance (EPR) analysis indicated that SO and OH radicals were the main active species in MB degradation. Meanwhile, the possible MB degradation mechanism was proposed. After four catalytic cycles, the degradation efficiency of MB has not been greatly reduced, indicating the practical application potential of CoFeO/ZIF-8 in water pollution cleanup.
10.1016/j.chemosphere.2019.125021
Heterostructured TiO@HKUST-1 for the enhanced removal of methylene blue by integrated adsorption and photocatalytic degradation.
Xiaobo Min,Xinyu Li,Jie Zhao,Xiaoxian Hu,Weichun Yang
Environmental technology
Aiming at exploring an effective photocatalytic adsorbent for organic dye removal, a series of heterostructured TiO@HKUST-1 photocatalysts, by incorporating HKUST-1 with different TiO nanoparticles loading, were prepared by single-step hydrothermal method. The morphology and surface characteristics of the as-prepared TiO@HKUST-1were analyzed using SEM, HRTEM, XRD, FTIR, UV-vis DRS, and Photoluminescence techniques. The adsorption-photocatalytic degradation of the model dye methylene blue (MB) on the catalysts was investigated. It was indicated that the introduction of a certain amount of TiO on the surface of HKUST-1 could improve the transfer and separation of the photogenerated charge carriers, resulting in the enhanced photocatalytic activity. The optimal 0.02TiO@HKUST-1 exhibited the highest MB removal rate with about 4.4 and 19.3 times as high MB removal efficiency as that of HKUST-1 and TiO, respectively. Heterostructured TiO@HKUST-1 materials for the removal of MB involved the integrated adsorption and visible light photocatalysis. Meanwhile, the composite exhibited good reusability in the process of cyclic experiments. Therefore, this work provides a potential MOF-based photocatalytic adsorbent for organic dye removal.
10.1080/09593330.2020.1745295
Enhanced visible light photocatalytic degradation of dyes in aqueous solution activated by HKUST-1: performance and mechanism.
RSC advances
HKUST-1 is a copper-based metal-organic framework (MOF) and potential photocatalyst, but minimal research has addressed the performance and mechanism of HKUST-1 in the visible light photocatalytic degradation of dyes. In the present work, HKUST-1 was applied as a photocatalyst to activate peroxomonosulfate (PMS) under visible light (Vis) for dye removal in aqueous solution. The results showed that the removal efficiency of two cationic dyes [rhodamine B (RhB) and methylene blue (MB)] was greater than 95% within 120 min. Free radicals such as SO ˙, ·OH were present in the degradation process, with SO ˙ playing a dominant role. Zeta potential, X-ray photoelectron spectroscopy, and photoluminescence spectroscopy data were used to investigate the degradation mechanism. In the degradation process, surface charge attraction between HKUST-1 and cationic dyes promotes removal efficiency, with the degradation efficiency of cationic dyes (MB and RhB) more than 50% higher than for anionic dyes [acid orange 7 (AO) and methyl red (MR)]. On the other hand, HKUST-1 has been proved to activate PMS by conducting photoelectrons, which accelerated the degradation of dyes. Compared with the reaction conditions of PMS/Vis, when the HKUST-1 was present (HKUST-1/PMS/Vis), the degradation rates of MB and RhB increased by 62.7 and 63.2%, respectively.
10.1039/d0ra05275b
Highly efficient Fenton and enzyme-mimetic activities of NH-MIL-88B(Fe) metal organic framework for methylene blue degradation.
Scientific reports
Here, we show that NH-MIL-88B(Fe) can be used as a peroxidase-like catalyst for Fenton-like degradation of methylene blue (MB) in water. The iron-based NH-MIL-88B(Fe) metal organic framework (MOF) was synthesized by a facile and rapid microwave heating method. It was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, powder X-ray diffraction, and the Brunauer-Emmett-Teller method. The NH-MIL-88B(Fe) MOF possesses intrinsic oxidase-like and peroxidase-like activities. The reaction parameters that affect MB degradation were investigated, including the solution pH, NH-MIL-88B(Fe) MOF and HO concentrations, and temperature. The results show that the NH-MIL-88B(Fe) MOF exhibits a wide working pH range (pH 3.0-11.0), temperature tolerance, and good recyclability for MB removal. Under the optimal conditions, complete removal of MB was achieved within 45 min. In addition, removal of MB was above 80% after five cycles, showing the good recyclability of NH-MIL-88B(Fe). The NH-MIL-88B(Fe) MOF has the features of easy preparation, high efficiency, and good recyclability for MB removal in a wide pH range. Electron spin resonance and fluorescence probe results suggest the involvement of hydroxyl radicals in MB degradation. These findings provide new insight into the application of high-efficient MOF-based Fenton-like catalysts for water purification.
10.1038/s41598-018-23557-2
Bimetallic metal-organic frameworks anchored corncob-derived porous carbon photocatalysts for synergistic degradation of organic pollutants.
Sun Zhe,Wu Xiaoliang,Qu Keqi,Huang Zhanhua,Liu Shouxin,Dong Mengyao,Guo Zhanhua
Chemosphere
Metal-organic frameworks (MOFs) are promising for photocatalysis owing to their excellent structure and performance. Unfortunately, poor stability in both aqueous solutions and high temperatures and lack of adsorption centers during reactions limit their practical applications. Herein, a bimetallic MOF anchored corncob calcined derived activated carbon (CCAC) was successfully prepared by a one-step solvothermal method. Benefiting from unique structures and synergetic effect, the porous carbon provided a high specific surface area for stable MOF support and served as an organic pollutant buffer-reservoir, which was advantageous for efficient photocatalytic degradation of organic pollutants. The optimized MOF/CCAC-5 samples possessed excellent visible light degradation rate, i.e., 100% for Rh B, more than 96% for six mixed dyes, and 98% for tetracycline. This prominent photocatalytic activity was caused by active species, including photoelectrons (e), photo-holes (h) and superoxide free radicals (•O). The transient photocurrent response and electrochemical impedance tests showed that MOF/CCAC-5 exhibited a relatively high charge separation and low carrier recombination rate. Cyclic and simulation experiments indicated high reusability, stability and universality of the composite photocatalysts. These exciting results provide new pathways for the fabrication of MOFs anchored porous carbon materials.
10.1016/j.chemosphere.2020.127389
Trifunctional metal-organic platform for environmental remediation: structural features with peripheral hydroxyl groups facilitate adsorption, degradation and reduction processes.
Kaur Harpreet,Kumar Rakesh,Kumar Ajay,Krishnan Venkata,Koner Rik Rani
Dalton transactions (Cambridge, England : 2003)
A Cd(ii)-based metal-organic framework (MOF) {[Cd(PA)(4,4'-bpy)2](H2O)}n (where, PA = pamoic acid, and bpy = bipyridine) has been demonstrated to have trifunctional properties, namely as (i) an efficient and selective adsorbent for dyes, (ii) a visible-light-active photocatalyst for the degradation of dyes and (iii) a photocatalyst for Cr(vi) reduction. Hence, this material has a very good potential for application in environmental remediation. In particular, the MOF exhibits excellent selectivity toward cationic methylene blue (MB) dye adsorption and its separation over neutral (neutral red) and anionic (methyl orange) dyes. In addition, the catalyst has also been explored for the photocatalytic degradation of less adsorbed dyes, such as methyl orange (MO) and rhodamine B (RhB). Subsequently, the potential of the presented MOF for the photocatalytic reduction of Cr(vi) under visible light irradiation has also been investigated and the catalyst was found to reduce 95% of Cr(vi) within 3 h. Moreover, simultaneous one-pot photocatalytic reduction of Cr(vi) and dye degradation has been demonstrated with high efficiency using the same catalyst. The mechanism of adsorption could be correlated to the presence of peripheral hydroxyl groups in the MOF and the photocatalytic activity observed under visible light could be attributed to the optical properties of Cd-MOF. In principle, this work could broaden the utilization of single metal organic platform for multifunctional applications toward environmental remediation.
10.1039/c8dt04180f
Effect of Cu-based metal organic framework (Cu-MOF) loaded with TiO2 on the photocatalytic degradation of rhodamine B dye.
Xue Xiaoxiao,Weng Yujing,Yang Shicheng,Meng Shihang,Zhang Zhengting,Yi Guiyun,Zhang Yulong
Environmental science and pollution research international
Using copper nitrate trihydrate as the copper source, TiO2@Cu-MOF nanocomposites were prepared by a one-step crystallization method, and the effect of the amount of TiO2 loaded on the adsorption of rhodamine B was studied. X-ray diffraction (XRD), scanning electron microscope (SEM), energy spectrometer (EDS), N adsorption-desorption (BET), and infrared spectroscopy (FTIR) were used to characterize the microstructure and surface properties of composite materials. The results show that the composite material not only has a good degradability for rhodamine B, the decolorization rate reaches 98.03% after 120 min, but it also maintains a good cycle performance. Fitting the first-order kinetic equation to the reaction process, under the optimal conditions, R = 0.98, indicating that the reaction process conforms to the first-order kinetic equation. Therefore, the catalyst has good catalytic degradation and cycle performance.
10.1007/s11356-020-11805-w
Sonophotocatalytic degradation of trypan blue and vesuvine dyes in the presence of blue light active photocatalyst of Ag3PO4/Bi2S3-HKUST-1-MOF: Central composite optimization and synergistic effect study.
Mosleh S,Rahimi M R,Ghaedi M,Dashtian K
Ultrasonics sonochemistry
An efficient simultaneous sonophotocatalytic degradation of trypan blue (TB) and vesuvine (VS) using Ag3PO4/Bi2S3-HKUST-1-MOF as a novel visible light active photocatalyst was carried out successfully in a continuous flow-loop reactor equipped to blue LED light. Ag3PO4/Bi2S3-HKUST-1-MOF with activation ability under blue light illumination was synthesized and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), photoluminescence (PL) and diffuse reflectance spectra (DRS). The effect of operational parameters such as the initial TB and VS concentration (5-45mg/L), flow rate (30-110mL/min), irradiation and sonication time (10-30min), pH (3-11) and photocatalyst dosage (0.15-0.35g/L) has been investigated and optimized using central composite design (CCD) combined with desirability function (DF). Maximum sonophotodegradation percentage (98.44% and 99.36% for TB and VS, respectively) was found at optimum condition set as: 25mg/L of each dye, 70mL/min of solution flow rate, 25min of irradiation and sonication time, pH 6 and 0.25g/L of photocatalyst dosage. At optimum conditions, synergistic index value was obtained 2.53 that indicated the hybrid systems including ultrasound irradiation and photocatalysis have higher efficiency compared with sum of the individual processes.
10.1016/j.ultsonch.2016.04.007
Ultrasound-assisted synthesis of metal organic framework for the photocatalytic reduction of 4-nitrophenol under direct sunlight.
Samuel Melvin S,Bhattacharya Jayanta,Parthiban C,Viswanathan Gayathri,Pradeep Singh N D
Ultrasonics sonochemistry
In this study, the metal organic framework MOF [Zn(BDC)(DMF)] crystal was synthesized via ultrasonic irradiation and solvothermal method. The synthesized MOF [Zn(BDC)(DMF)] crystal was characterized by PXRD, FTIR, FESEM-EDX, TGA, UV-DRS and BET. The catalytic activity of MOF [Zn(BDC)(DMF)] was investigated by 4-nitrophenol (4-NP) degradation under direct sunlight irradiation. The influence of various degradation parameters such as initial 4-NP concentration, dosage, pH and HO concentration were investigated. The results indicated that the synthesized MOF [Zn(BDC)(DMF)] exhibited strong photocatalytic activity in the presence of NaBH under sunlight irradiation and the reduction of 4-NP to 4-aminophenol (4-AP) completed within 10 min. The study provides the synthesized MOF [Zn(BDC)(DMF)] crystal can be used as a high performance catalyst for the treatment of dyes in wastewater.
10.1016/j.ultsonch.2018.08.004
In-situ development of metal organic frameworks assisted ZnMgAl layered triple hydroxide 2D/2D hybrid as an efficient photocatalyst for organic dye degradation.
Bhuvaneswari K,Palanisamy G,Pazhanivel T,Maiyalagan T,Shanmugam P,Grace Andrews Nirmala
Chemosphere
Metal organic framework (MOF) supported layered triple hydroxide (LTH) 2D/2D hybrid material was prepared by a simple hydrothermal method. The photophysical properties of the prepared samples were investigated through a set of analytical methods such as X-ray diffraction, Fourier-transform infrared spectroscopy, field emission scanning electron microscope, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy and mapping. The photocatalytic degradation activity of as prepared 2D/2D MOF-5/LTH hybrid sample was investigated against methylene blue (MB) dye under the UV-visible light irradiation. The degradation efficiency of the MOF-5/LTH hybrid sample was twice a time greater than that of pristine MOF-5, particularly degradation efficiency of the MOF-5, LTH and MOF-5/LTH hybrid samples are 43.3, 57.7 and 98.1% respectively. The Pseudo first order rate and the reusing investigation was further used to study the catalytic activity and stability of the as-synthesized 2D/2D photocatalyst. The observed improvement in the photocatalytic activity of the hybrid samples were owed to enhance visible light absorption, efficient separation and transportation of photoinduced electrons and holes.
10.1016/j.chemosphere.2020.128616
Synergistic adsorption and photocatalytic degradation of persist synthetic dyes by capsule-like porphyrin-based MOFs.
Wang Na,Liu Siyang,Sun Zhongqiao,Han Yide,Xu Junli,Xu Yan,Wu Junbiao,Meng Hao,Zhang Bingsen,Zhang Xia
Nanotechnology
The synergistic effects involving surface adsorption and photocatalytic degradation commonly play significant roles in the removal of persistent synthetic organics from wastewater in the case of porous semiconductors. Inspired by the visible-light harvesting advantages of porphyrin-based MOFs, a capsule-like bimetallic porphyrin-based MOF (PCN-222(Ni/Hf)) has been successfully constructed through a facile hydrothermal method. In which, the Hf (IV) ions were exactly bonded to the carboxyl groups substituted on the porphyrin rings, meanwhile the Ni (II) ions were finely bonded to the -N inside the porphyrin rings. The adsorption/photocatalytic performances were assessed by using four persistent dyes including rhodamine B (RhB), basic violet 14 (BV14), crystal violet, and acid black 210 (AB210) as the target substances, and enhanced total removal efficiency was obtained by the bimetallic PCN-222(Ni/Hf) in comparison with that of single PCN-222(Hf). The electrochemical analyses and the sacrificial agent capture experiments were carried out to elucidate the photocatalytic mechanism, and the adsorption/photocatalytic stability of PCN-222(Ni/Hf) is also investigated. The work has broadened the applications of porphyrin-based MOFs in the removal of organics by combining their excellent surface adsorption capacity and photocatalytic activities.
10.1088/1361-6528/ac162e
Atomically dispersed Fe/Bi dual active sites single-atom nanozymes for cascade catalysis and peroxymonosulfate activation to degrade dyes.
Chen Qiumeng,Liu Yuan,Lu Yuwan,Hou Yuejie,Zhang Xiaodan,Shi Wenbing,Huang Yuming
Journal of hazardous materials
Constructing single-atom nanozymes (SAzymes) with densely exposed and dispersed double metal-N catalytic sites for pollution remediation remains rare and challenging. Herein, we report a novel Fe-Bi bimetallic MOF-derived carbon supported Fe-N and Bi-N dual-site FeBi-NC SAzyme for cascade catalysis and peroxymonosulfate activation to degrade dye pollutants, which is synthesized from the Fe-doped Bi-MOF as a precursor. The formation of both Fe-N and Bi-N sites is demonstrated by XANES and EXAFS. The FeBi-NC SAzyme has high single atoms loadings of Fe (2.61 wt%) and Bi (8.01 wt%), and displays 5.9- and 9.8-fold oxidase mimicking activity enhancement relative to the Fe-NC and Bi-NC SAzymes, respectively. When integrated acetylcholinesterase (AChE) and FeBi-NC SAzyme, a cascade enzyme-nanozyme system is developed for selective and sensitive screening of AChE activity with a low detection limit of 1 × 10 mU mL. Both Fe-N and Bi-N in FeBi-NC display a strong binding energy and electron donating capability to promote peroxymonosulfate activation to generate highly active intermediates for rhodamine B degradation. 100% rhodamine B removal occurs within 5 min via FeBi-NC mediated activation of peroxymonosulfate. The DFT calculations reveal that high activity of FeBi-NC is due to the isolated Fe-N and Bi-N sites and their synergy.
10.1016/j.jhazmat.2021.126929
Enhanced photocatalytic performance of UiO-66-NH/TiO composite for dye degradation.
Mansouri Mohsen,Sadeghian Samira,Mansouri Ghobad,Setareshenas Naimeh
Environmental science and pollution research international
In this study, the performance of TiO, ZnO, UiO-66-NH and UiO-66-NH/TiO nanoparticles was investigated. They apply as photocatalysts for the destruction of organic reactive red dye 120 (RR120) under UV light. In order to determine the optimal conditions, effects of different catalysts and initial dye concentration, HO content and catalyst loading parameters were examined. Taguchi-designed experimental method was used to obtain optimal test conditions. The physical and chemical properties of synthetic photocatalysts were investigated by SEM, XRD, EDX, BET and DRS. SEM images show that the globular particles of titania are well placed on the surface of the metal-organic framework (MOF). XRD and EDX analyses also confirmed the presence of titania in the synthesised UiO-66-NH/TiO photocatalyst. Optimal values of HO, pH, the amount of catalyst, the dye concentration and the type of available photocatalyst to remove the RR120 dye, were obtained by 80 μl/l, 3 mg/l, 5 mg/l and 20 mg/l, UiO-66-NH/TiO catalyst, respectively. The required time for complete removal of RR120 dye under detection limit of 0.136 mg/l in optimal conditions was 10 min. The RR120 photocatalytic degradation followed the first-order kinetic equation according to the Langmuir-Hinshelwood model (k = 0.407 min). The result of optimisation showed the 20 wt% of the titania on MOF (UiO-66-NH) photocatalyst can be used in advanced oxidation processes, and it can be used as a suitable option for cleaning coloured effluent.
10.1007/s11356-020-12098-9
Selective detection of sulfasalazine antibiotic and its controllable photodegradation into 5-aminosalicylic acid by visible-light-responsive metal-organic framework.
Dalton transactions (Cambridge, England : 2003)
The extensive use of sulfasalazine (SSZ) antibiotics has brought potential threats to aquatic ecosystems and human health. Thus, necessary measures for the removal of SSZ must be taken to prevent arbitrary antibiotic exposure to the aquatic environment. However, not all the recent photocatalysts that have been used for the degradation of SSZ could not achieve the controlled release of SSZ and hence are losing their medicinal values. Herein, by utilizing an Eosin Y moiety as an efficient light-harvesting and emission site, an Eosin Y-based visible-light-responsive metal-organic framework has been synthesized and characterized, which exhibits high selectivity for detecting the antibiotic SSZ in water and simulated physiological conditions, with a detection limit of below 1 μM (0.4 μg mL). It also represents the first example of a MOF-based photocatalyst for the controllable degradation of SSZ into 5-aminosalicylic acid with excellent catalytic activity and recyclability.
10.1039/d2dt01270g
Gold and palladium supported on an ionic liquid modified Fe-based metal-organic framework (MOF) as highly efficient catalysts for the reduction of nitrophenols, dyes and Sonogashira-Hagihara reactions.
RSC advances
Two supported noble metal species, gold and palladium anchored on an ionic liquid-modified Fe-based metal-organic framework (MOF), were successfully synthesized and characterized by FT-IR, XRD, TEM, XPS, SEM, EDX, and elemental mapping. The ionic liquid post-modified MOF was used for anchoring Au or Pd at ppm levels, and the resulting materials were employed as catalysts in the reduction of nitrophenol isomers, dyes, and Sonogashira-Hagihara reactions. Using the Au@Fe-MOF-IL catalyst, reduction of nitrophenol isomers, as well as the reductive degradation of dyes, , methylene blue (MB), methyl orange (MO), and methyl red (MR) were performed efficiently in water. On the other hand, Pd@Fe-MOF-IL was used as an effective catalyst in the Sonogashira-Hagihara coupling reaction of aryl iodides and bromides using very low amounts of Pd. These catalysts were recycled and reused for several runs without deteriorating remarkably in catalytic performance.
10.1039/d3ra00283g
Metal-organic frameworks with different oxidation states of metal nodes and aminoterephthalic acid ligand for degradation of Rhodamine B under solar light.
Pattappan Dhanaprabhu,Vargheese Stella,Kavya K V,Kumar R T Rajendra,Haldorai Yuvaraj
Chemosphere
Metal-organic frameworks (MOFs) have been investigated recently as effective visible light photocatalysts. In this report, we synthesized nickel, iron, and titanium-based MOFs with different oxidation states of metal ions and aminoterephthalic acid ligand for photocatalytic degradation of Rhodamine B (RhB) dye under solar light irradiation. The photoluminescence analysis revealed that the Fe-MOF could suppress the recombination of photoinduced charges and effectively degrade the dye. The photocatalytic experiment demonstrated that the Fe-MOF exhibited higher degradation efficiency of dye (90 %) compared to the Ni-MOF (9 %) and Ti-MOF (50 %) at pH 7 in 90 min. In addition, the effects of catalyst amount, dye concentration, and solution pH on dye degradation were investigated. The photodegradation of dye using Fe-MOF was well-fitted to the first-order kinetics with an R value of 0.9987. Furthermore, reactive oxygen species test and electron paramagnetic resonance study revealed that the superoxide anion radicals were mainly responsible for the dye degradation. Cyclic test analysis indicates that there was no substantial decrease in the degradation efficiency of dye after four consecutive cycles.
10.1016/j.chemosphere.2021.131726
InS nanoparticles coupled to In-MOF nanorods: The structural and electronic modulation for synergetic photocatalytic degradation of Rhodamine B.
Hu Lin,Mao Dong,Yang Liu-Han,Zhu Ming-Sheng,Fei Zheng-Hao,Sun Shi-Xin,Fang Dong
Environmental research
Enhancing photocatalytic performance via electronic modulation have attracted much attention for synergetic photocatalytic degradation of antibiotic pollutant. In this study, a new hetero-structured system is raised, which comprises InS coupled to In-MOF and operates as an efficient photocatalyst for RhB degradation. The formation of hetero-structure and occurred electron modulation of InS/In-MOF hybrid was confirmed by relevant characterizations. Surprisingly, the InS/In-MOF hybrid represented enhanced photocatalytic ability over In-MOF. The photocatalysis of Rhodamine B in presence of InS/In-MOF hybrid has achieved 92.2 % degradation.
10.1016/j.envres.2021.111874
MOF-derived core/shell C-TiO/CoTiO type II heterojunction for efficient photocatalytic removal of antibiotics.
Lin Biyun,Li Shanshan,Peng Yannan,Chen Zhihong,Wang Xin
Journal of hazardous materials
A novel core/shell C-TiO/CoTiO type II heterojunction was successfully synthesized via a direct calcination method by using MIL-125/Co core-shell nanocakes as a sacrificial template and precursor. In the calcination process, the organic ligand in MIL-125 acts as an in-situ carbon doping source to form a carbon-doped TiO core (C-TiO). At the same time, CoTiO nanoparticles are formed on the surface of C-TiO by an in-situ solid-state reaction between the C-TiO and Co shell of MIL-125/Co. Due to such delicate core/shell structural features, carbon doping and type II heterojunctions, C-TiO/CoTiO core/shell composites can effectively harvest visible light, facilitate the interfacial separation and suppress the recombination of photogenerated electron-hole pairs, leading to the remarkable photocatalytic activity for removal of ciprofloxacin (CIP). In particular, C-TiO/CoTiO-3 exhibits the best photocatalytic degradation activity of CIP with a degradation efficiency of 99.6% and a total carbon content removal percentage of 76% under visible-light illumination for 120 min. In addition, the proposed photocatalytic mechanism study illustrated that the main radical species in the photocatalytic degradation of CIP using C-TiO/CoTiO as the photocatalyst is •OH. This work provides a new approach and insight for synthesizing core/shell heterojunction-based photocatalysts for various applications.
10.1016/j.jhazmat.2020.124675
Gold Nanorods/Metal-Organic Framework Hybrids: Photo-Enhanced Peroxidase-Like Activity and SERS Performance for Organic Dyestuff Degradation and Detection.
Analytical chemistry
Metal-organic frameworks (MOFs) are widely used to mimic enzymes for catalyzing chemical reactions; however, low enzyme activity limit their large-scale application. In this work, gold nanorods/metal-organic frameworks (Au NRs/Fe-MOF) hybrids were successfully synthesized for photo-enhanced peroxidase-like catalysis and surface-enhanced Raman spectroscopy (SERS). The enzyme-like activity of Au NRs/Fe-MOF hybrids was significantly enhanced under localized surface plasmon resonance (LSPR), because the hot electrons produced on Au NRs surface were transferred into Fe-MOF, activating the Fenton reaction by Fe/Fe conversion and preventing the recombination of hot electrons and holes. This photo-enhanced enzyme-like catalytic performance was investigated by X-ray photoelectron spectrometry (XPS), electrochemical analysis, activation energy measurement, and in situ Raman spectroscopy. Afterward, Methylene Blue (MB) was chosen to demonstrate the photo-enhanced peroxidase-like performance of Au NRs/Fe-MOFs. The Au NRs/Fe-MOF caused chemical and electromagnetic enhancement of Raman signals and exhibited a great potential for the detection of toxic chemicals and biological molecules. The detection limit of MB concentration is 9.3 × 10 M. In addition, the Au NRs/Fe-MOF hybrids also showed excellent stability and reproducibility for photo-enhanced peroxidase-like catalysis. These results show that nanohybrids have great potential in many fields, such as sensing, cancer therapy, and energy harvesting.
10.1021/acs.analchem.2c00036
Synthesis, structure and photocatalytic degradation of organic dyes of a copper(II) metal-organic framework (Cu-MOF) with a 4-coordinated three-dimensional CdSO topology.
Qian Lin Lu,Wang Zhi Xiang,Tian Hai Xin,Li Min,Li Bao Long,Li Hai Yan
Acta crystallographica. Section C, Structural chemistry
Metal-organic frameworks (MOFs) have attracted much interest in the fields of gas separation and storage, catalysis synthesis, nonlinear optics, sensors, luminescence, magnetism, photocatalysis gradation and crystal engineering because of their diverse properties and intriguing topologies. A Cu-MOF, namely poly[[(μ-succinato-κO:O'){μ-tris[4-(1,2,4-triazol-1-yl)phenyl]amine-κN:N'}copper(II)] dihydrate], {[Cu(CHO)(CHN)]·2HO} or {[Cu(suc)(ttpa)]·2HO}, (I), was synthesized by the hydrothermal method using tris[4-(1,2,4-triazol-1-yl)phenyl]amine (ttpa) and succinate (suc), and characterized by IR, powder X-ray diffraction (PXRD), luminescence, optical band gap and valence band X-ray photoelectron spectroscopy (VB XPS). Cu-MOF (I) shows a twofold interpenetrating 4-coordinated three-dimensional CdSO topology with point symbol {6·8}. It presents good photocatalytic degradation of methylene blue (MB) and rhodamine B (RhB) under visible-light irradiation. A photocatalytic mechanism was proposed and confirmed.
10.1107/S2053229619009306
Porphyrin-Based Two-Dimensional Layered Metal-Organic Framework with Sono-/Photocatalytic Activity for Water Decontamination.
ACS nano
Water treatment is crucial to improve the water quality and reduce diarrheal and chronological diseases caused by excessive discharge of organic dyes and other waste. The development and expansion of efficient catalysts for the degradation and sterilization of organic dyes has attracted widespread attention. Herein, we report an example of a porphyrin-based two-dimensional layered metal-organic framework (MOF) (2DZnTcpp) and its efficient sono-/photocatalytic degradation of organic dyes and bactericidal activity. The dislocated layers effectively avoid close π-π stacking and provide a porous space for oxygen/water/dye contact. The introduction of Zn ions increases the spin orbital coupling through the heavy atom effect and promotes the intersystem crossing process for singlet oxygen generation. The effective ligand-to-metal charge transfer and the excessive open Zn catalytic sites also facilitate water splitting for hydroxyl radical generation. These features together promote the reactive oxygen species (ROS) generation of 2DZnTcpp under light illumination or ultrasound sonication. It is worth noting that the 2DZnTcpp with a high specific surface area and porosity shows efficient sono-/photocatalytic degradation of organic dye waste. Moreover, 2DZnTcpp could also largely inactivate under light irradiation (the light power of 1 sun) or ultrasound sonication for 30 min with efficiencies over 99.99999%. This work provides an approach for the design and synthesis of MOF-based sono-/photocatalysts used in the purification and treatment of textile wastewater and is committed to the establishment of a more efficient, fast, and environmentally friendly catalytic system.
10.1021/acsnano.1c09301
Synthesis characterization of Zn-based MOF and their application in degradation of water contaminants.
Water science and technology : a journal of the International Association on Water Pollution Research
Metal-organic frameworks (MOFs) are currently popular porous materials with research and application value in various fields such as medicine and engineering. Aiming at the application of MOFs in photocatalysis, this paper mainly reviews the main synthesis methods of ZnMOFs and the latest research progress of Zn MOF-based photocatalysts to degrade organic pollutants in water, such as organic dyes. This nanomaterial is being used to treat wastewater and has proven to be very efficient because of its exceptionally large surface area and porous nature. The results show that Zn-MOFs are capable of high degradation of the above pollutants and over 90% of degradation was observed in publications. In addition, the reusability percentage was examined and studies showed that the Zn-MOF nanostructure has very good stability and can continue to degrade a high percentage of pollutants after several cycles. This review focuses on Zn-MOFs and their composites. First, the methods of synthesis and characterization of these compounds are given. Finally, the application of these composites in the process of photocatalytic degradation of dye pollutants such as methylene blue, methyl orange, crystal violet, rhodamine B, etc. is explained.
10.2166/wst.2022.318
Degradation of azo dyes under visible light with stable MOF based on tetrastyrene imidazole ligand.
Zhang Xiao,Wang Lu-Jie,Han Zhen,Meng Xing,Wang Hai-Ning,Zhou Zi-Yan,Su Zhong-Min
Dalton transactions (Cambridge, England : 2003)
In the present work, a new 3D metal-organic framework (MOF) has been synthesized and characterized. The MOF exhibits good chemical stability in aqueous solutions with the pH scale ranging from 3 to 11. Interestingly, the MOF shows high catalytic activities for the degradation of azo dyes (MO, CR and CBR) under visible light without H2O2. The Ea values of the MOF for MO, CR and CBR degradation are obtained to be 23.49, 52.68 and 15.19 kJ mol-1, respectively. In addition, the MOF can be reused in the catalytic process without the catalytic activity decreasing obviously.
10.1039/d0dt00415d
Composite of MOF and chitin as an efficient catalyst for photodegradation of organic dyes.
Sadjadi Samahe,Koohestani Fatemeh,Mahmoodi Niyaz Mohammad,Rabeie Bahareh
International journal of biological macromolecules
A novel composite has been fabricated by using MOF and chitin as a natural and biocompatible compound. To this purpose, MOF was synthesized by using 2-aminoterephthalic acid and iron (III) chloride hexahydrate and then reacted with Cl-functionalized chitin. The resulting composite was characterized and utilized as a catalyst for degradation of methylene blue both in dark condition and under visible light irradiation. The results indicated superior catalytic activity under visible light irradiation. Furthermore, study of the reaction variables, including basicity, dye concentration and catalyst loading showed that the highest catalytic activity was achieved at basic condition. It was also found that both initial dye concentration and catalyst loading can affect the catalytic activity. To disclose the merits of the composite compared to its individual components, kinetic studies of the photo-degradation process in the presence of the composite, chitin and MOF have been performed. The results confirmed superior activity the composite compared to its components. The study of the mechanism of the reaction using scavengers confirmed that the created holes (h) are the most effective species in the process of photocatalytic degradation of MB. Notably, the catalyst was recyclable and could be used for degradation of other dyes.
10.1016/j.ijbiomac.2021.04.034
Self-Assembly of a 3D Hollow BiOBr@Bi-MOF Heterostructure with Enhanced Photocatalytic Degradation of Dyes.
Xu Mei-Ling,Jiang Xiao-Jie,Li Jia-Ran,Wang Fu-Ji,Li Kui,Cheng Xin
ACS applied materials & interfaces
Considering the flexibility, adjustable pore structure, and abundant active sites of metal-organic frameworks (MOFs), rational design and fine control of the MOF-based hetero-nanocrystals is a highly important and challenging subject. In this work, self-assembly of a 3D hollow BiOBr@Bi-MOF microsphere was fabricated through precisely controlled dissociation kinetics of the self-sacrificial template (BiOBr) for the first time, where the residual quantity of BiOBr and the formation of Bi-MOF were carefully regulated by changing the reaction time and the capability of coordination. Meanwhile, the hollow microstructure was formed in BiOBr@Bi-MOF through the Oswald ripening mechanism to separate photogenerated electron-hole pairs and increase the adsorption capacity of Bi-MOF for dyes, which significantly enhanced the photocatalytic degradation efficiency of RhB from 56.4% for BiOBr to 99.4% for the optimal BiOBr@Bi-MOF microsphere. This research broadens the selectivity of semiconductor/MOF hetero-nanocrystals with reasonable design and flexible synthesis.
10.1021/acsami.1c16612
Superparamagnetic MOF@GO Ni and Co based hybrid nanocomposites as efficient water pollutant adsorbents.
Ventura Karen,Arrieta Roy A,Marcos-Hernández Mariana,Jabbari Vahid,Powell Camilah D,Turley Reagan,Lounsbury Amanda W,Zimmerman Julie B,Gardea-Torresdey Jorge,Wong Michael S,Villagrán Dino
The Science of the total environment
A series of highly efficient adsorbents were developed using Ni(BTC) and Co(BTC) metal-organic frameworks (MOFs) and FeO magnetic nanoparticles (MNPs) to functionalize graphene oxide (GO). XRD results show high crystallinity of the prepared nanomaterials and the successful decoration of Ni(BTC) and Co(BTC) MOFs over the GO substrate (BTC = benzene-1,3,5-tricarboxylic acid). SEM and TEM imaging show the successful formation of nanoscale MOFs and FeO MNPs over GO. IR spectroscopy supports the characterization and successful preparation of the FeO/MOF@GO hybrid composite nanoadsorbents. The prepared composite nanoadsorbents were used to sorb Methylene Blue (MB) as a model for common organic pollutants in water and common ions (Na, Ca, Mg, SO, SiO) from a brackish water model. The adsorbed concentration at equilibrium of MB of the prepared composite nanoadsorbents increases by an average of 30.52 and 13.75 mg/g for the Co and Ni composite, respectively, when compared to the MOFs parent materials. The adsorbed amount of sulfate ions increases by 92.1 mg/g for the Co composite and 112.1 mg/g for the Ni composite, when compared to graphene oxide. This adsorption enhancement is attributed to suppressed aggregation through increased dispersive forces in the MOFs due to the presence of GO, formation of nanoscale MOFs over the GO platform, and the hindering of stacking of the graphene layers by the MOFs. Leaching tests show that the release of Co and Ni ions to water is reduced from 105.2 and 220 mg/L, respectively, in the parent MOF materials to 0.5 and 16.4 mg/L, respectively, in the composite nanoadsorbents. These findings show that the newly developed composite nanoadsorbents can sorb organic pollutants, and target sulfate and silicate anions, which makes them suitable candidates for water and wastewater treatments.
10.1016/j.scitotenv.2020.139213
Ethylenediamine-functionalized Zr-based MOF for efficient removal of heavy metal ions from water.
Ahmadijokani Farhad,Tajahmadi Shima,Bahi Addie,Molavi Hossein,Rezakazemi Mashallah,Ko Frank,Aminabhavi Tejraj M,Arjmand Mohammad
Chemosphere
Ethylenediamine-functionalized Zr-based metal-organic framework (MOF, UiO-66-EDA) was prepared via Michael addition reaction to investigate its potential for adsorption of heavy metal ions from water. Specifically, the influence of agitation time, solution pH, the dosage of the adsorbent, initial metal ion concentration, temperature, and coexistence of other metal ions was investigated on the removal efficiency of UiO-66-EDA towards Pb(II), Cd(II), and Cu(II) metal ions. The pseudo-second-order kinetic model governed the adsorption of these ions onto the UiO-66-EDA. Langmuir isotherm model matched the experimental isotherm of adsorption with a maximum adsorption capacity of 243.90, 217.39, and 208.33 mg/g for Pb, Cd, and Cu ions, respectively. The adsorption of Pb, Cd, and Cu ions onto UiO-66-EDA was dependent on electron exchange, electron sharing, electrostatic and covalent interactions between the metal ions as well as the abundant functional groups on UiO-66-EDA surface. Thermodynamic parameters such as free energy changes (ΔG), standard enthalpy changes (ΔH), and standard entropy changes (ΔS) were calculated, which revealed spontaneous and endothermic nature of the adsorption process. The UiO-66-EDA was stable and recyclable during adsorption studies of Pb, Cd, and Cu ions, suggesting its potentiality as an adsorbent for heavy metals recovery.
10.1016/j.chemosphere.2020.128466
Solvent-Driven Transformation of Zn/Cd-Deoxycholate Assemblies.
Smith Rachelle M S,Amiri Mehran,Martin Nicolas P,Lulich Alice,Palys Lauren N,Zhu Guomin,De Yoreo James J,Nyman May
Inorganic chemistry
Deoxycholic acid (DOC) is a unique, biologically derived surfactant with facial amphiphilicity that has been exploited, albeit minimally, in supramolecular assembly of materials. Here, we present the synthesis and structural characterization of three hybrid metal (Zn and Cd)-DOC compounds. Analysis by single-crystal X-ray diffraction reveals the many interactions that are possible between these facial surfactants and the influence of solvent molecules that drive the assembly of materials. These structures are the first metal-DOC complexes besides those obtained from alkali and alkaline earth metals. We isolated polymeric chains of both Cd and Zn ( and ) from water. Major interactions between DOC molecules in these phases are hydrophobic in nature. exhibits unique 1 symmetry, with complete interdigitation of the amphiphiles between neighboring polymeric chains. , obtained from methanol dissolution of , features the OZn tetrahedron, widely known in basic zinc acetate and MOF-5 (metal organic framework). We document a solvent-driven, room-temperature transition between and (in both directions) by scanning and transmission electron microscopies in addition to small-angle X-ray scattering, powder X-ray diffraction, and infrared spectroscopy. These studies show the methanol-driven transition of to occurs via an intermediate with no long-range order of the Zn clusters, indicating the strongest interactions driving assembly are intramolecular. On the contrary, water-driven solid-to-solid transformation from to exhibits crystal-to-crystal transformation. is robust, easy to synthesize, and comprised of biologically benign components, so we demonstrate dye absorption as a proxy for water treatment applications. It favors absorption of positively charged dyes. These studies advance molecular level knowledge of the supramolecular assembly of facial surfactants that can be exploited in the design of organic-inorganic hybrid materials. This work also highlights the potential of solvent for tuning supramolecular assembly processes, leading to new hybrid materials featuring facial surfactants.
10.1021/acs.inorgchem.1c02245
Direct synthesis of MOF-derived nanoporous carbon with magnetic Co nanoparticles toward efficient water treatment.
Torad Nagy L,Hu Ming,Ishihara Shinsuke,Sukegawa Hiroaki,Belik Alexis A,Imura Masataka,Ariga Katsuhiko,Sakka Yoshio,Yamauchi Yusuke
Small (Weinheim an der Bergstrasse, Germany)
Nanoporous carbon particles with magnetic Co nanoparticles (Co/NPC particles) are synthesized by one-step carbonization of zeolitic imidazolate framework-67 (ZIF-67) crystals. After the carbonization, the original ZIF-67 shapes are preserved well. Fine magnetic Co nanoparticles are well dispersed in the nanoporous carbon matrix, with the result that the Co/NPC particles show a strong magnetic response. The obtained nanoporous carbons show a high surface area and well-developed graphitized wall, thereby realizing fast molecular diffusion of methylene blue (MB) molecules with excellent adsorption performance. The Co/NPC possesses an impressive saturation capacity for MB dye compared with the commercial activated carbon. Also, the dispersed magnetic Co nanoparticles facilitate easy magnetic separation.
10.1002/smll.201302910
Facile preparation of nanocellulose/Zn-MOF-based catalytic filter for water purification by oxidation process.
Zhu Wenkai,Han Minsu,Kim Donggyun,Zhang Yang,Kwon Goomin,You Jungmok,Jia Chong,Kim Jeonghun
Environmental research
Sulfate radical (SO)-based advanced oxidation processes (SR-AOPs) have recently attracted much attention due to their potential in degrading organic pollutants. Metal-organic frameworks (MOFs) have been reported as effective materials to generate SO. However, it is challenging to separate and recover the dispersed MOF particles from the reaction solution when MOFs are used alone. We used cellulose nanofibers (CNFs) as a porous filter template to immobilize Zn-based MOF, zeolitic imidazolate framework-8 (ZIF-8), and obtained a catalytic composite membrane having peroxymonosulfate (PMS) activating function to produce SO. The CNF was effective in holding ZIF-8 nanoparticle and making a durable porous filter. The activated PMS-produced OH and SO radicals from ZIF-8 play an important role in the catalytic reaction. More than 90% of methylene blue and rhodamine B was degraded by ZIF-8/CNFs composite membrane in the PMS environment within 60 min. The ZIF-8/CNFs catalytic filters can be used several times without performance reduction for organic dye degradation. The results show that ZIF-8/CNFs catalytic membrane can be separated from organic pollution system quickly and used for the efficient separation and recovery of MOF particle-based catalytic materials. Therefore, this study provides a new perspective for fabricating the MOFs particles-immobilized catalytic filter by biomass nanocellulose-based materials for water purification. This method can be used for facile fabrication of the cellulose-based porous functional filter and open diverse applications.
10.1016/j.envres.2021.112417
Cerium based UiO-66 MOF as a multipollutant adsorbent for universal water purification.
Rego Richelle M,Sriram Ganesan,Ajeya Kanalli V,Jung Ho-Young,Kurkuri Mahaveer D,Kigga Madhuprasad
Journal of hazardous materials
Herein, we demonstrate the use of cerium (Ce)-UiO-66 metal organic framework (MOF) for the removal of a variety of potentially toxic pollutants. The Ce-UiO-66 MOF, with similar framework topologies to Zr-UiO-66, has not been explored for its adsorptive properties in water remediation. The replacement of Zr metal center with Ce yields a MOF that can be synthesized in shorter durations with lesser energy consumptions and with excellent multipollutant adsorption properties. Further, the Ce-UiO-66 MOF was also studied for its adsorption abilities in the binary component system. Interestingly, the adsorbent showed higher adsorption capacities in the presence of other pollutants. Removal studies for other potentially toxic anionic and cationic dyes showed that the Ce-UiO-66 MOF has a wide range of contaminant removal abilities. Investigations of individual adsorption capacities revealed that the Ce-UiO-66 MOF has a maximum adsorption capacity of 793.7 mg/g for congo red (CR), 110 mg/g for methylene blue (MB), 66.1 mg/g for fluoride (F), 30 mg/g for Cr and 485.4 mg/g for the pharmaceutical waste diclofenac sodium (DCF). To imply the practical applications of the Ce-UiO-66 MOF we have also demonstrated an adaptable filter that could separate all the potentially toxic pollutants.
10.1016/j.jhazmat.2021.125941
Novel MOF-808 metal-organic framework as highly efficient adsorbent of perfluorooctane sulfonate in water.
Journal of colloid and interface science
Perfluorooctane sulfonate (PFOS) is a highly persistent contaminant of emerging concern causing harmful effects to human and ecosystem health. In this study, a novel MOF-808 metal-organic framework (MOF) was prepared and evaluated for adsorptive removal of PFOS from aqueous solution. The MOF-808 had high specific surface area (SSA; 1610 m/g) and was structurally stable in aqueous medium for 7 days under different pH conditions. The MOF-808 reached PFOS adsorption equilibrium within 30 min (at 500 mg/L initial PFOS) and attained the maximum adsorption capacity of 939 mg/g at pH 4.1 - 5.4 (with 50 - 500 mg/L initial PFOS). The PFOS adsorption capacity of MOF-808 was unaffected at pH 2 to 7, but gradually decreased at pH > 7. High SSA, favorable pore size and abundant active adsorption sites on MOF-808 triggered high PFOS adsorption onto the adsorbent. The PFOS adsorption process was endothermic and spontaneous in nature. Electrostatic interaction between the cationic central cluster ([ZrO(OH)]) of MOF-808 and PFOS anion was identified as the key mechanism of PFOS adsorption onto MOF-808, as evident from the infrared spectroscopic investigation of the adsorbent. This study suggests that MOF-808 can be considered as a highly efficient adsorbent for PFOS removal from water and warrants future research to evaluate the application and performance of the material under wastewater conditions.
10.1016/j.jcis.2022.05.050
Fe-Loaded MOF-545(Fe): Peroxidase-Like Activity for Dye Degradation Dyes and High Adsorption for the Removal of Dyes from Wastewater.
Zhang Chuang,Li Haichao,Li Chen,Li Zhengqiang
Molecules (Basel, Switzerland)
Methods to remove dye pollutants with natural enzyme, like horseradish peroxidase (HRP), are still limited due to high costs and low stability levels. The development of such a method with similar enzymatic activity is important and could be helpful in wastewater disposal. A metal organic framework material, Fe-loaded MOF-545 (Fe), was synthesized in our study as a new way to remove dyes due to its peroxidase-like activity. The structural characterizations of Fe-loaded MOF-545(Fe) was investigated using scanning electron microscopy (SEM), UV-Vis absorption spectra, and X-ray diffraction (XRD). The peroxidase-like (POD-like) activity of Fe-loaded MOF-545(Fe) was investigated under different pH and temperature conditions. Because of the Fe added into the MOF-545 structure, the absorption of Fe-loaded MOF-545(Fe) for acid (anionic) dyes (methyl orange (MO)) was better than for basic (cationic) dyes (methylene blue (MB)). The Fe-loaded MOF-545(Fe) could give a significant color fading for MO and MB over a short time (about two hours) with peroxidase-like activity. The remarkable capacity of Fe-loaded MOF-545(Fe) to remove the MO or MB is due to not only physical adsorption, but also degradation of the MO and MB with POD-like activity. Therefore, Fe-loaded MOF-545(Fe) has significant potential regarding dye removal from wastewater.
10.3390/molecules25010168
Efficient degradation of organic dye using Ni-MOF derived NiCo-LDH as peroxymonosulfate activator.
Ramachandran Rajendran,Thangavel Sakthivel ,Minzhang Li ,Haiquan Shan ,Zong-Xiang Xu ,Wang Fei
Chemosphere
Nickel-based metal-organic framework (Ni-MOF) was employed as a sacrificial template for the preparation of nickel-cobalt layered double hydroxide (NiCo-LDH) under different hydrolysis time. The template etching rate varied at different hydrolysis time, resulting in variations of the structural and morphology of NiCo-LDHs. The NiCo-LDH/10 sample showed a large specific surface area and the well-oriented larger dimension of thinner sheets due to the sufficient in-situ etching of the Ni-MOF template. The NiCo-LDH/10 was an excellent heterogeneous catalyst to activate peroxymonosulfate (PMS) for highly efficient Reactive Red-120 dye degradation. The results exhibited that the degradation efficiency of the NiCo-LDH/10-PMS catalyst was 89% for RR-120 dye within 10 min in the presence of the PMS system, which is higher than other NiCo-LDHs. Moreover, the other influencing factors such as PMS concentration, catalyst dosage, initial pH were also investigated towards degradation. The radical quenching measurement proved that the sulfate (SO) and hydroxyl (OH) had been indicated as the primary radicals. Besides, the NiCo-LDH/10-PMS catalyst showed excellent reusability even after five consecutive cycles (83.6% of the degradation efficiency). This work offer insight study on the construction of controlled morphology NiCo-LDH heterogeneous structure for high-efficiency PMS activation.
10.1016/j.chemosphere.2020.128509