Project description:Introducing hierarchical pore structure to microporous materials such as metal-organic frameworks (MOFs) can be beneficial for reactions where the rate of reaction is limited by low rates of diffusion or high pressure drop. This advantageous pore structure can be obtained by defect formation, mostly via post-synthetic acid etching, which has been studied extensively on water-stable MOFs. Here we show that a water-unstable HKUST-1 MOF can also be modified in a corresponding manner by using phosphoric acid as a size-selective etching agent and a mixture of dimethyl sulfoxide and methanol as a dilute solvent. Interestingly, we demonstrate that the etching process which is time- and acidity- dependent, can result in formation of defective HKUST-1 with extra interconnected hexagonal macropores without compromising on the bulk crystallinity. These findings suggest an intelligent scalable synthetic method for formation of hierarchical porosity in MOFs that are prone to hydrolysis, for improved molecular accessibility and diffusion for catalysis.
Project description:Removing organic contaminants such as dyes from water is essential to purify wastewater. Herein, zeolitic imidazolate framework-8 (ZIF-8) and ZnO@N-doped C are reported as effective adsorbents and photocatalysts for the adsorption and degradation of organic dyes. The materials showed effective and selective adsorption toward anionic dyes such as methyl blue (MeB) dye in the presence of fluorescein (FLU) dye. The adsorption capacities of ZnO@N-doped C for MeB and FLU dyes are 900 mg g-1 and 100 mg g-1, respectively. According to UV-Vis diffuse reflectance spectroscopy (DRS) data, ZnO@N-doped C has a lower bandgap (2.07 eV) than ZIF-8 (4.34 eV) and ZnO (3.12 eV). Thus, ZnO@N-doped C serves as an effective photocatalyst for the degradation of both dyes under UV exposure. The degradation efficiency capacity of the dye (50 mg L-1) is >90% using 200 mg L-1 of the photocatalyst. The mechanism of adsorption and photocatalysis is investigated. The photodegradation pathway of the dye involved the generation of oxidative hydroxy radicals (OH˙), which can degrade the dyes. The degradation products of FLU were recorded using mass spectrometry.
Project description:Currently, finding high capacity adsorbents with large selectivity to capture Xe is still a great challenge. In this work, nitrogen-doped porous carbons were prepared by programmable temperature carbonization of zeolitic imidazolate framework-8 (ZIF-8) and ZIF-8/xylitol composite precursors and the resultant samples are marked as Carbon-Z and Carbon-ZX, respectively. Further adsorption measurements indicate that ZIF-derived nitrogen-doped Carbon-ZX exhibits extremely high Xe capacity of 4.42 mmol g(-1) at 298 K and 1 bar, which is higher than almost all other pristine MOFs such as CuBTC, Ni/DOBDC, MOF-5 and Al-MIL-53, and even more than three times of the matrix ZIF-8 at similar conditions. Moreover, Carbon-ZX also shows the highest Xe/N2 selectivity about ~120, which is much larger than all other reported MOFs. These remarkable features illustrate that ZIF-derived nitrogen-doped porous carbon is an excellent adsorbent for Xe adsorption and separation at room temperature.
Project description:This work reports a new approach for the synthesis of a zeolitic imidazolate framework (ZIF-8) composite. It employs the direct growth of the crystalline ZIF-8 on a mixed-metal oxide support TiO2-SiO2 (TSO), which mimics the porous structure of Populus nigra. Using the natural leaf as a template, the TSO support was prepared using a sol-gel method. The growth of the ZIF-8 layer on the TSO support was carried out by the seeds and second growth method. This method facilitates the homogeneous dispersion of ZIF-8 crystals at the surface of the TSO composite. The ZIF-8@TSO composite adsorbs methanol selectively, mainly due to the hierarchical porous structure of the mixed oxide support. As compared with the as-synthesized ZIF-8, a 50% methanol uptake is achieved in the ZIF-8@TSO composite, with only 25 wt % ZIF-8 loading. IAST simulations show that the ZIF-8@TSO composite has a preferential adsorption toward methanol when using an equimolar methanol-ethanol mixture. An opposite behavior is observed for the as-synthesized ZIF-8. The results show that combining MOFs and mixed-oxide supports with bioinspired structures opens opportunities for synthesizing new materials with unique and enhanced adsorption and separation properties.
Project description:In this work, a consecutive adsorption-catalysis approach to remove Cu2+ ions and catalytic reduction of 4-nitrophenol (4-NP) is proposed. Attapulgite (ATP) nanorods are utilized as adsorbents to enrich Cu2+ ions from contaminated water. Subsequently, the adsorbed ions were in situ reduced to construct Cu-loaded ATP catalysts. The catalytic activities of the composite ATP-Cu catalysts are evaluated by 4-NP reduction in the presence of NaBH4. The optimal ATP-Cu50 sample prepared by putting ATP into a 50 mg L-1 CuSO4 solution could complete the catalytic reaction within 4 min. Moreover, the Cu-deposited ATP nanorods can be integrated into a continuous flow catalytic system, and the 4-NP can be rapidly reduced. This method sheds lights on the fabrication of ATP-based hybrid catalysts and the removal of multiple water pollutants.
Project description:The 3D hierarchical porous 7MgO·2B2O3·7H2O (MBH) microspheres were prepared by a phase transformation of chloropinnoite firstly, and anhydrous α-3MgO·B2O3 (MBA) microspheres were obtained by thermal conversion of 7MgO·2B2O3·7H2O, and then β-3MgO·B2O3 (MBB) microspheres were obtained by phase conversion of α-3MgO·B2O3. All samples were characterized by XRD, FT-IR, TG and SEM. The microsphere nanostructures with a hierarchical porous structure were assembled by nanosheets with a thickness of 20-30 nm, and the growth mechanisms were also proposed. By using N2 adsorption-desorption, the specific surface areas were measured as 103.62 m2 g-1 for MBH and 46.10 m2 g-1 for MBA. They exhibited excellent selective adsorption performance for Congo red (CR) with maximum adsorption capacities of 202.84 and 170.07 mg g-1 respectively, and the corresponding adsorption mechanisms were also investigated. The adsorption processes were well fitted with the pseudo-second-order rate equation and Langmuir adsorption model. In addition, the corresponding adsorption thermodynamic parameters were also calculated. It is necessary to highlight that the hierarchical porous microspheres could be considered as promising candidates for removal of CR dye pollutants.
Project description:A novel pyrolysis char (PC), prepared by H3PO4 catalytic pyrolysis of oily sludge (OS), was presented to remove methylene blue (MB) dye from aqueous solution for the first time. The optimal preparation conditions (catalytic pyrolysis temperature of 411 °C, H3PO4 impregnation ratio of 2.44, and catalytic pyrolysis time of 59 min) were predicted by the response surface methodology. The optimal PC exhibited favorable hierarchical porous properties, which brought a large adsorption capability (322.89 mg/g). The adsorption process fitted well with the Langmuir model and pseudo-second order model. In addition, thermodynamic parameters showed that the adsorption process was endothermic (ΔH 0 > 0) and spontaneous (ΔG 0 < 0). The adsorption capability was strongly influenced by coexisting metal ions due to the competitive adsorption effect. The inhibition for MB adsorption was arranged in the following order: Al3+ > Fe3+ > Mg2+ > Ca2+ > K+ > Na+. The adsorption mechanism of MB onto the OS-derived PC includes pore filling, π-π interactions, and electrostatic interactions. The as-obtained PC adsorbent exhibited good reusability performance, which leads to great potential in practical application for wastewater treatment.
Project description:Due to rapid socioeconomic development, increased phosphorus concentrations can cause eutrophication of water bodies, with devastating effects on environmental sustainability and aquatic ecosystems. In this study, ZIF-8-PhIm was prepared for phosphorus removal using 2-phenylimidazole via the solvent-assisted ligand exchange (SALE) method. The structure and composition of ZIF-8-PhIm were characterized by various methods, including X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), 1H nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), and Brunauer-Emmett-Teller (BET) analysis. Compared to the ZIF-8 material, it exhibited a multistage pore structure with larger pore capacity and pore size, increased hydrophilicity, exposure of more adsorption sites, and also stronger electrostatic interaction. Under optimized conditions (T = 298 K, C0 = 150 mg/L, dose = 0.2 g/L), the adsorption capacity of ZIF-8-PhIm reached 162.93 mg/g, which was greater than that of the ZIF-8 material (92.07 mg/g). The Langmuir isotherm and pseudo-second-order kinetic models were suitable for describing the phosphate adsorption of ZIF-8-PhIm. The main effects of ZIF-8-PhIm on phosphate adsorption were Zn-O-P bonding and electrostatic interactions. It also had good regeneration properties. The ZIF-8-PhIm/CS spheres were prepared using chitosan (CS) as the cross-linking agent. The results of dynamic adsorption experiments on the spheres showed a saturation capacity of 85.69 mg/g and a half-penetration time of 514.15 min at 318 K according to the fitted results.
Project description:Biomass waste treatment and detrimental dye adsorption are two of the crucial environmental issues nowadays. In this study, we investigate to simultaneously resolve the aforementioned issues by synthesizing chitosan sponges as adsorbents toward rose bengal (RB) dye adsorption. Through a temperature-controlled freeze-casting process, robust and recyclable chitosan sponges are fabricated with hierarchical porosities resulted from the control of concentrations of chitosan solutions. Tested as the adsorbents for RB, to the best of our knowledge, the as-prepared chitosan sponge in this work reports the highest adsorption capacity of RB (601.5 mg/g) ever. The adsorption mechanism, isotherm, kinetics, and thermodynamics are comprehensively studied by employing statistical analysis. Importantly and desirably, the sponge type of chitosan adsorbents exceedingly facilitates the retrieving and elution of chitosan sponges for recyclable uses. Therefore, the chitosan sponge adsorbent is demonstrated to possess dramatically squeezable capability with durability for 10,000 cycles and recyclable adsorption for at least 10 cycles, which provides an efficient and economical way for both biomass treatment and water purification.
Project description:Novel hierarchical porous carbon materials (HPCs) were fabricated via a reactive template-induced in situ hypercrosslinking procedure. The effects of carbonization conditions on the microstructure and morphology of HPCs were investigated, and the adsorption of methylene blue (MB) on HPCs was explored. The as-prepared HPCs has a hierarchical micro-, meso- and macropore structure, which results from the overlap of hollow nanospheres possessing microporous shells and macroporous cavities. The carbonization temperature, carbonization time and carbonization heating rate played important roles in tailoring the nanostructures of HPCs. The BET specific surface area and micropore specific surface area can reach 2388 m2 g-1 and 1892 m2 g-1, respectively. Benefitting from the well-developed pore structure, the MB removal efficiency can exceed 99% under optimized conditions. The adsorption kinetics and thermodynamics can be well described by a pseudo-second-order model and Langmuir model, respectively. Furthermore, such adsorption was characterized by a spontaneous endothermic process.