Search Results (88)

Four different MIL-68(Al) catalysts were synthesized and characterized by XPS, SEM, TEM, XRD, DLS, Nitrogen adsorption removal, and other methods. An aluminum-based MOF (Metal Organic Framework) (MIL-68(Al))/graphite oxide (GO) composite with TiO₂ showed the largest BET specific area with best adsorption performance. Representation demonstrated that MIL-68(Al) and TiO₂ nanoparticles are uniformly dispersed on the surface of the GO lamellar, and a tight heterojunction structure is formed between them. The MIL-68(Al)/GO/TiO₂ exhibits good pore characteristics, structural morphology, and catalytic performance. Adsorption experiments of methyl orange can reach 99.7% with the effect of MIL-68(Al)/GO/TiO₂ in water for 20 min. Moreover, the pH range can be applied to 1–13 and a high concentration of 200 mg/L methyl orange solution also worked well. In addition, this kind of catalyst can also be used for rhodamine B, methylene blue, congo red, and tetracycline in 20 min with good adsorption. Meanwhile, simple filtration can quickly recover MIL-68(Al)/GO/TiO₂ and effectively reuse it. Free radical capture experiments showed a large number of •OH radicals during the adsorption of MO (Methyl Orange) solution by MIL-68(Al)/GO/TiO₂. Meanwhile, the electrostatic interaction, π-π packing and hydrogen bonding make MIL-68(Al)/GO/TiO₂ have a higher adsorption capacity for MO. Therefore, co-doping optimized the structure of MIL-68(Al), enhancing its stability in strong acids and bases while improving adsorption performance across a broader pH range than previously reported. This work addresses the instability of MIL-68(Al) under extreme conditions, demonstrating its significant potential for wastewater treatment applications. Full article

The FeZn-MOFs@Al₂O₃ catalyst was synthesized under solvothermal conditions. Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), temperature-programmed desorption of ammonia (NH₃-TPD), and specific Brunauer–Emmett–Teller (BET) surface area and pore volume were used to systematically investigate the effects of different parameters such as molar ratio of iron to zinc, synthesis temperature, and synthesis time on the properties of the materials. The results showed that the optimum synthesis conditions of FeZn-MOFs@Al₂O₃ composites were 140 °C for 1 h, and the optimum molar ratio of Fe³⁺ and Zn²⁺ was 1.3:0.7. Under the aforesaid conditions, FeZn-MOFs@Al₂O₃ had the deacidification rate of vacuum gas oil (VGO) up to 96.3%. The optimum esterification parameters were as follows: the amounts of catalyst and ethylene glycol were, respectively, 2.5 wt% and 4.0 wt% of the sample oil, the reaction temperature was 250 °C, and the reaction time was 1 h. Full article

The thermocatalytic hydrogenation of CO₂ to methanol offers a promising route for reducing greenhouse gas emissions (GHG) and producing valuable chemicals and fuels. In this study, copper–zinc bimetallic catalysts supported on a zirconium-based MOF-808 framework were synthesized via a facile deposition–precipitation method and compared to a conventional Cu/ZnO/Al₂O₃ (CZA) catalyst. MOF-808 was selected due to its high surface area and porous structure, which enhance metal dispersion. Characterization through X-ray diffraction (XRD) and N₂ physisorption showed significant changes in surface area and pore structure after Cu-Zn incorporation and calcination. The 50-CuZn MOF-808 catalyst achieved the best catalytic performance at 260 °C and 40 bar, demonstrating a high STY of 193.32 gMeOH·Kgcat⁻¹ h⁻¹ and a turnover frequency (TOF) of 47.44 h⁻¹, surpassing traditional CZA catalysts. The strong Cu-Zn-Zr interactions within the MOF-808 framework played a crucial role in promoting CO₂ activation and methanol formation. This study underscores the potential of MOF-808-supported Cu-Zn catalysts as viable alternatives to traditional systems for CO₂ hydrogenation to methanol. Full article

Considering the importance of organic functionalization of MOFs, we here report a simple, tunable and efficient one-step post-modification procedure for introducing amino and carboxylic groups into the mesoporous metal–organic framework Al- and Cr-MIL-101-NH₂ based on its reaction with alkyl bromides. This procedure allows also access to polyfunctionalized MIL-101 decorated with both carboxylic and primary amino groups. Other chemical functions, such as alcohols and alkynes, were also successfully introduced by this method. Full article

Dry reforming has gained widespread attention among CO₂ utilization approaches, as it is able to convert both CO₂ and CH₄ into syngas, thus mitigating global warming. Moreover, dielectric barrier discharge (DBD) non-thermal catalytic plasma reactors are potential technologies for CO₂ and CH₄ conversion, due to their low energy consumption and ease of operation. Catalysts also play an important role in ensuring optimal performance. For instance, metal–organic frameworks (MOFs) such as ZIF-8, NH₂-UiO-66(Zr), and NH₂-MIL-53(Al) are rarely reported in the literature for plasma technologies in dry reforming, despite their strong attributes such as high surface area and charge characteristics. In this work, these MOF catalysts were synthesized and characterized to evaluate their internal morphology, crystallinity, and surface area. Characterization studies showed that ZIF-8, NH₂-UiO-66(Zr), and NH₂-MIL-53(Al) generally showed similar properties to those results reported in the literature. Additionally, based on DBD catalytic plasma testing, NH₂-UiO-66(Zr) with an input power of 30 W recorded the highest H₂ and CO yields of 3.20% and 2.34%, respectively, at a CO₂:CH₄ molar ratio of 7:3. These values could be referred to for future studies on the improvement of MOF catalysts performance in dry reforming under the plasma processes prior to upscaling. Full article

As the most promising techniques for refractory antibiotic degradation in wastewater management, sulfate radical-based advanced oxidation processes (SR-AOPs) have attracted considerable attention. However, systematic studies on potassium peroxymonosulfate (PMS) activation by MOF-derived metal oxides coated with LDH materials are still lacking. In this work, a series of catalysts consisting of CoCu-MOFs coated with CuAl/LDH were synthesized for PMS activation in the removal of sulfamethoxazole (SMX). As expected, CoCu-MOFs coated with CuAl/LDH catalyst showed high SMX removal and stability in PMS activation. In the CoCu/LDH/PMS reaction, the SMX removal was nearly 100% after 60 min, and the mineralization reached 53.7%. The catalyst showed excellent catalytic stability and low metal leaching concentrations (Co: 0.013 mg/L, Cu: 0.313 mg/L), as detected by ICP. Sulfate radicals and hydroxyl radicals were identified as the dominant reactive species in the CoCu/LDH/PMS system. Moreover, the presence of ¹O₂ in the process revealed the coupling of non-radical and radical processes. The XPS results showed that the layered structure of CoCu/LDH promoted the recycling of metal ions (high and low valence), which facilitated heterogeneous PMS activation. The effects of different reaction conditions and reuse cycles were also determined. The SMX oxidation pathways were proposed based on the intermediates identified by LC/MS. The high activity and stability of CoCu/LDH provide a new mechanistic understanding of PMS activation catalysts and their potential utilization in practical wastewater treatment. Full article

The application of metal–organic frameworks (MOFs) has attracted increasing attention in organic synthesis. The modification of MOFs can efficiently tailor the structure and improve the property for meeting ongoing demand in various applications, such as the alteration of gas adsorption and separation, catalytic activity, stability, and sustainability or reusability. In this study, carboxyethylsilanetriol (CEST) disodium salt was used as a dual-functional ligand for modified Al-MIL-53 to fabricate CEST-functionalized Al-MIL-53 samples through a hydrothermal reaction of aluminum nitrate, terephthalic acid, and CEST disodium salt by varying the molar ratio of CEST to terephthalic acid and keeping a constant molar ratio of Al³⁺/-COOH of 1:1. The structure, composition, morphology, pore feature, and stability were characterized by XRD, different spectroscopies, electron microscopy, N₂ physisorption, and thermogravimetric analysis. With increasing CEST content, CEST-Al-MIL-53 still preserves an Al-MIL-53-like structure, but the microstructure changed compared with pure Al-MIL-53 due to the integration of CEST. Such a CEST-Al-MIL-53 was used as the support to load Pd particles and afford a catalyst Pd/CEST-Al-MIL-53 for Suzuki–Miyaura C-C cross-coupling reaction of aryl halides and phenylboronic acid under basic conditions. The resulting Pd/CEST-Al-MIL-53 showed a high catalytic activity compared with Pd/Al-MIL-53, due to the nanofibrous structure of silicon species-integrated CEST-Al-MIL-53. The nanofiber microstructure undergoes a remarkable transformation into intricate 3D cross-networks during catalytic reaction, which enables the leachable Pd particles to orientally redeposit and inlay into these networks as the monodisperse spheres and thereby effectively preventing Pd particles from aggregation and leaching, therefore demonstrating a high catalytic performance, long-term stability, and enhanced reusability. Obviously, the integration of CEST into MOFs can effectively prevent the leaching of active Pd species and ensure the re-deposition during catalysis. Moreover, catalytic performance strongly depended on catalyst dosage, temperature, time, solvent, and the type of the substituted group on benzene ring. This work further extends the catalytic application of hybrid metal–organic frameworks. Full article

CeO₂-supported noble metal catalysts show great application potential in the catalytic oxidation of volatile organic compounds and hazardous organic wastewater. In this paper, an efficient Ru/CeO₂ catalyst is developed by combining the oxygen affinity of noble metals and the redox of supports for catalytic wet air oxidation (CWAO) of reconstituted tobacco wastewater. First, what factors affect the catalytic performance are studied by investigating the effect of supports (C, TiO₂, Al₂O₃, and CeO₂) and noble metals (Pt, Pd, and Ru) on the activity. Second, the catalytic performance of Ru/CeO₂ is further enhanced by tuning the morphology of CeO₂ supports. The results indicate that the Ru/CeO₂-R (rod-like) catalyst is highly active and can reach a high TOC conversion of 97.6% at 220 °C in 1 h. In contrast, the TOC conversions of Ru/CeO₂-MOF, Ru/CeO₂-NP (nanoparticle), and Ru/CeO₂-C (cube-like) are 93.3, 77.9, and 68.2%, respectively. Ru/CeO₂-R also presented good stability. The TOC conversion can be maintained at approximately 85% in four consecutive cycles. The characterization results indicate that better Ru dispersion, higher Ce³⁺ content, more surface reactive oxygen species, electron transfer between Ru and CeO₂-R, and oxygen transfer from CeO₂-R to Ru are the main reasons for the best catalytic performance of the Ru/CeO₂-R catalyst. Full article

Metal–organic frameworks (MOFs) are hybrid inorganic–organic 3D coordination polymers with metal sites and organic linkers, which are a “hot” topic in the research of sorption, separations, catalysis, sensing, and environmental remediation. In this study, we explore the molecular mechanism and kinetics of interaction of the new copper porphyrin aluminum metal–organic framework (actAl-MOF-TCPPCu) compound 4 with a vapor of the volatile organic sulfur compound (VOSC) diethyl sulfide (DES). First, compound 4 was synthesized by post-synthetic modification (PSM) of Al-MOF-TCPPH₂ compound 2 by inserting Cu²⁺ ions into the porphyrin ring and characterized by complementary qualitative and quantitative chemical, structural, and spectroscopic analysis. Second, the interaction of compound 4 with DES vapor was analyzed dynamically by the novel method of in situ time-dependent attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy at controlled humidity levels. The sorbent–adsorbate interactions, as analyzed by the shifts in IR peaks, indicate that the bonding includes the hydroxy O-H, carboxylate COO⁻, and phenyl groups. The kinetics of sorption obeys the Langmuir pseudo-first-order rate law. The pre-adsorption of water vapor by compound 4 at the controlled relative humidity under static (equilibrium) conditions yields the binary stoichiometric adsorption complex (Al-MOF-TCPPCu)_1.0(H₂O)_8.0. The pre-adsorption of water vapor makes the subsequent sorption of DES slower, while the kinetics obey the same rate law. Then, static pre-adsorption of water vapor was followed by static sorption of DES vapor, and the ternary adsorption complex (Al-MOF-TCPPCu)_1.0(H₂O)_8.0(DES)₃.₈ was obtained. Despite the pre-adsorption of significant amounts of water, the binary complex adsorbs a large amount of DES: ca. 36.6 wt. % (per compound 4). Finally, the ternary complex is facilely regenerated by gentle heating under vacuum. Compound 4 and related MOFs are promising for adsorptive removal of vapor of DES and related VOSCs from dry and humid air. Full article

The aim of this work is to compare the traditional uniaxial pressing with an innovative shaping technique, Digital Light Processing (DLP), in the preparation of porous mullite (3Al₂O₃·2SiO₂) supports to be functionalized with an active coating for CO₂ capture. Indeed, the fabrication of complex geometries with 3D-printing technologies allows the production of application-targeted solid sorbents with increased potentialities. Therefore, this research focused on the effect of the purity of the selected raw materials and of the microstructural porosity of 3D-printed ceramic substrates on the Metal Organic Frameworks (MOFs) coating efficiency. Two commercial mullite powders (Mc and Mf) differing in particle size distribution (D₅₀ of 9.19 µm and 4.38 µm, respectively) and iron oxide content (0.67% and 0.38%) were characterized and used to produce the substrates, after ball-milling and calcination. Mc and Mf slurries were prepared with 69 wt% of solid loading and 5 wt% of dispersant: both show rheological behavior suitable for DLP and good printability. DLP 3D-printed and pressed pellets were sintered at three different temperatures: 1350 °C, 1400 °C and 1450 °C. Mf 3D-printed samples show slightly lower geometrical and Archimedes densities, compared to Mc pellets, probably due to the presence of lower Fe₂O₃ amounts and its effect as sintering aid. Mullite substrates were then successfully functionalized with HKUST-1 crystals by a two-step solvothermal synthesis process. Ceramic substrate porosity, depending on the shaping technique and opportunely tuned controlling the sintering temperature, was correlated with the functionalization efficiency in terms of MOFs deposition. Three-dimensional-printed substrates exhibit a higher and more homogeneous HKUST-1 uptake compared to the pressed pellets as DLP introduces desirable porosities able to enhance the functionalization. Therefore, this work provides preliminary guidelines to improve MOFs coating on mullite surfaces for CO₂ capture applications, by opportunely tuning the substrate porosity. Full article

Tetratoluene has the following three isomers: durene (DR), prehnitene (PR), and isodurene (IR). DR and PR often coexist during the separation of C10 heavy aromatics at different levels. They are both important organic chemical raw materials and their separation is the key to the high-efficiency industrial utilization of C10 heavy aromatics. In this paper, six metal–organic frameworks (MOFs), including ZU-61, MIL-101, UIO-66, UIO-66-NH₂, Mg-MOF-74, and MIL-53(Al), were used as the adsorbents of DR and PR. Their skeletons were structurally optimized using VASP software (latest v. 6.4.3). The adsorption capacity and isosteric heats of both pure components and mixtures (the molar ratio was 1:1) in gas were calculated using Grand Canonical Monte Carlo simulation from 10 kPa to 300 kPa at 298 K. The results indicated that all adsorption processes were physical. ZU-61, UIO-66, UIO-66-NH₂, and Mg-MOF-74 presented suitable capacity differences for DR and PR at 300 kPa. The selectivity values of these frameworks were all above 1.5. Thus, the four MOFs were prepared using the solvothermal method and characterized by SEM and XRD. Then, the competitive adsorption of DR and PR in liquid on the four MOFs was carried out as well. The results showed good agreement with the simulation in general, with a lower adsorption attained capacity due to the different phase states of both DR and PR. This study can guide the separation of tetratoluene isomers in C10 heavy aromatics. Full article

This study synthesized NiAl-layered double hydroxide (LDH)/Cu-MOF photocatalyst using a simple impregnation method involving NiAl-LDH and Cu-MOF. The successful synthesis was confirmed through Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), zeta potential measurements, thermogravimetric analysis (TGA), ultraviolet diffuse reflectance spectroscopy (UV-DRS), N₂ adsorption at −196 °C, and electrochemical impedance spectroscopy (EIS). Photocatalysts based on NiAl-LDH, Cu-MOF, and NiAl-LDH/Cu-MOF were used to remove methyl orange (MO) dye from contaminated water. The impact of various factors, including pH, dye concentration, and photocatalyst amount, on MO degradation efficiency was assessed. FTIR analysis was conducted both before and after dye degradation. The optimal degradation conditions were a photocatalyst dose of 25 mg and a pH of 3. Kinetic studies indicated that the degradation of MO dye onto NiAl-LDH/Cu-MOF followed a pseudo-first-order and an L–H or Langmuir–Hinshelwood model. The value of R² = 0.94 confirms the validity of pseudo-first-order and Langmuir–Hinshelwood (L–H) kinetic models for the photocatalytic degradation of MO dye. This study highlights the importance of developing novel photocatalysts with improved degradation efficiency to protect the water environment. Antibacterial activity was also performed with antibacterial sensibility testing by disk diffusion to determine minimal inhibitory and bactericidal concentrations. In short, NiAl-LDH/Cu-MOF can be helpful for various biomedical and industrial applications. Full article

Due to the increasing fluoride concentrations in water bodies, significant environmental concerns have arisen. This study focuses on aluminum-based materials with a high affinity for fluorine, specifically enhancing metal–organic frameworks (MOFs) with amino groups to improve their adsorption and defluorination performance. We systematically investigate the factors influencing and mechanisms governing the adsorption and defluorination behavior of amino-functionalized aluminum-based MOF materials in aqueous environments. An SEM, XRD, and FT-IR characterization confirms the successful preparation of NH₂-MIL-101 (Al). In a 10 mg/L fluoride ion solution at pH 7.0, fluoride ion removal efficiency increases with the dosage of NH₂-MIL-101 (Al), although the marginal improvement decreases beyond 0.015 g/L. Under identical conditions, the fluoride adsorption capacity of NH₂-MIL-101 (Al) is seven times greater than that of NH₂-MIL-101 (Fe). NH₂-MIL-101 (Al) demonstrates effective fluoride ion adsorption across a broad pH range, with superior fluoride uptake in acidic conditions. At a fluoride ion concentration of 7 mg/L, with 0.015 g of NH₂-MIL-101 (Al) at pH 3.0, adsorption equilibrium is achieved within 60 min, with a capacity of 31.2 mg/g. An analysis using adsorption isotherm models reveals that the fluoride ion adsorption on NH₂-MIL-101 (Al) follows a monolayer adsorption model, while kinetic studies indicate that the predominant adsorption mechanism is chemical adsorption. This research provides a scientific basis for the advanced treatment of fluoride-containing wastewater, offering significant theoretical and practical contributions. Full article