Defective hierarchical porous copper-based metal-organic frameworks synthesised via facile acid etching strategy

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.Comment: 14 pages, 8 figure

Effect of mono- and divalent extra-framework cations on the structure and accessibility of porosity in chabazite zeolites

Chabazite (CHA), one of the most common zeolite framework types, has a remarkable capacity to accommodate a wide range of different cations within the unique CHA framework. This has led to CHA being applied extensively in ion exchange, and studied for highly selective gas sorption, most notably through a trapdoor mechanism. Here, we report the systematic study of a series of six chabazite zeolites (i.e.K-CHA, Cs-CHA, Ca-CHA, Ba-CHA, Sr-CHA and Zn-CHA) obtained by subjecting the parent chabazite (KNa-CHA) to exchange operations with cations of different valences and atomic radii. These samples were examined using numerous techniques and it was found that the differences in valence and size between extra-framework cations exert a significant effect on the abundance of these cations positioned in the framework, resulting in differing nitrogen sorption ability measured in the synthesised chabazite zeolites. These findings will help to understand how the zeolite counter-cation affects the ability of the CHA material to selectively sequester and separate gases through the use of the trapdoor mechanism.</p

Effect of mono- and divalent extra-framework cations on the structure and accessibility of porosity in chabazite zeolites

Chabazite (CHA), one of the most common zeolite framework types, has a remarkable capacity to accommodate a wide range of different cations within the unique CHA framework. This has led to CHA being applied extensively in ion exchange, and studied for highly selective gas sorption, most notably through a trapdoor mechanism. Here, we report the systematic study of a series of six chabazite zeolites (i.e.K-CHA, Cs-CHA, Ca-CHA, Ba-CHA, Sr-CHA and Zn-CHA) obtained by subjecting the parent chabazite (KNa-CHA) to exchange operations with cations of different valences and atomic radii. These samples were examined using numerous techniques and it was found that the differences in valence and size between extra-framework cations exert a significant effect on the abundance of these cations positioned in the framework, resulting in differing nitrogen sorption ability measured in the synthesised chabazite zeolites. These findings will help to understand how the zeolite counter-cation affects the ability of the CHA material to selectively sequester and separate gases through the use of the trapdoor mechanism.</p

Designing a novel heterostructure AgInS₂@MIL-101(Cr) photocatalyst from PET plastic waste for tetracycline degradation

Semiconductor-containing porous materials with a well-defined structure could be unique scaffolds for carrying out selective organic transformations driven by visible light. We herein introduce for the first time a heterostructure of silver indium sulfide (AgInS(2)) ternary chalcogenide and a highly porous MIL-101(Cr) metal–organic framework (MOF) synthesised from polyethylene terephthalate plastic waste. Our results demonstrate that AgInS(2) nanoparticles were uniformly attached to each lattice plane of the octahedral MIL-101(Cr) structure, resulting in a nanocomposite with a high distribution of semiconductors in a porous media. We also demonstrate that the nanocomposite with up to 40% of AgInS(2) doping exhibited excellent catalytic activity for tetracycline degradation under visible light irradiation (∼99% tetracycline degraded after 4 h) and predominantly maintained its performance after five cycles. These results could promote a new material circularity pathway to develop new semiconductors that can be used to protect water from further pollution

Understanding the AC conductivity and permittivity of trapdoor chabazites for future development of next-generation gas sensors

Synthetic K+ chabazite (KCHA), Cs+ chabazite (CsCHA) and Zn2+ chabazite (ZnCHA) have been synthesized and investigated in order to relate the differences in their crystalline structures to their thermal stability, moisture content and frequency dependent alternating current (AC) conductivity, permittivity and phase angle at a range of temperatures. The materials are shown to exhibit the universal dielectric response, which is typical of materials consisting of both conductive and insulating regions. Due to the presence of porosity, the three chabazites were hydrated significantly at room temperature and so the dehydrated state was achieved by heating the chabazites to high temperatures to ensure that all different energetic types of water were removed. Cation migration activation energies for KCHA (0.66 ± 0.10) eV, CsCHA (0.88 ± 0.01) eV and ZnCHA (0.90 ± 0.01) eV were determined during the cooling cycle from the fully dehydrated state to provide an accurate measurement of the activation energies. Good thermal stability of the materials was observed up to 710 °C and below 200 °C the electrical properties can be strongly influenced by hydration level. Overall, it was determined that when either hydrated or dehydrated, KCHA had the highest conductivity and lowest cation migration activation energy of the three studied chabazites and thus has the most promising electrical properties for potential use as a gas sensing material in next-generation electrical-based gas sensors.</p

One-pot preparation of alumina-modified polysulfone-graphene oxide nanocomposite membrane for separation of emulsion-oil from wastewater

In recent years, polysulfone-based nanocomposite membranes have been widely used for contaminated water treatment because they comprise properties such as high thermal stability and chemical resistance. In this study, a polysulfone (PSf) nanocomposite membrane was fabricated using the wet-phase inversion method with the fusion of graphene oxide (GO) and alumina (Al2O3) nanoparticles. We also showed that GO-Al2O3 nanoparticles were synthesised successfully by using a one-pot hydrothermal method. The nanocomposite membranes were characterised by Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherms, energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), and water contact angle. The loading of GO and Al2O3 was investigated to improve the hydrophilic and oil rejection of the matrix membrane. It was shown that by using 1.5 wt.% GO-Al2O3 loaded in polysulfone, ~74% volume of oil was separated from the oil/water emulsion at 0.87 bar and 30 min. This figure was higher than that of the process using the unmodified membrane (PSf/GO) at the same conditions, in which only ~60% volume of oil was separated. The pH, oil/water emulsion concentration, separation time, and irreversible fouling coefficient (FRw) were also investigated. The obtained results suggested that the GO-Al2O3 nanoparticles loaded in the polysulfone membrane might have potential use in oily wastewater treatment applications