Highly Selective Carbonylation of CH3 Cl to Acetic Acid Catalyzed by Pyridine-Treated MOR Zeolite.

The selective conversion of methane to high value-added chemicals under mild conditions is of great significance for the commercially viable and sustainable utilization of methane but remains a formidable challenge. Herein, we report a strategy for efficiently converting methane to acetic acid via CH3 Cl as an intermediate. Up to 99.3 % acetic acid and methyl acetate (AA+MA) selectivity was achieved over pyridine-pretreated MOR (MOR-8) under moderate conditions of 523 K and 2.0 MPa. Water, conventionally detrimental to carbonylation reaction over zeolite catalysts, was conducive to the production of AA in the current reaction system. In the 100 h continuous test with the MOR-8 catalyst, the average AA+MA selectivity remained over 98 %. AA was formed by carbonylation of methoxy groups within 8-membered rings of MOR followed by hydrolysis. This strategy provided an approach for highly efficient utilization of methane to oxygenates under mild reaction conditions.

Directly decorated CeY zeolite for O2-selective adsorption in O2/N2 separation at ambient temperature.

The traditional zeolites used in air separation are generally N2-selective adsorbents. It was found for the first time that the O2/N2 adsorption selectivity can be reversed by directly decorating the Ce metal ion sites of a traditional Y zeolite with imidazole molecules, which results in a novel O2 adsorbent. The O2/N2 selectivity changes from 0.9 to 1.6 under normal conditions, and most importantly, the O2 adsorbent is recyclable. The in situ XPS characterization results indicate that the imidazole modification can change the electronic state of Ce in the Y zeolite and increase its affinity for O2, which is confirmed by theoretical calculations. Dynamic breakthrough adsorption experiments show that the adsorbent has significant application potential in air separation.

Efficient Separation of Xylene Isomers by a Pillar-Layer Metal-Organic Framework.

The separation of xylene isomers is one of the most challenging issues in the chemical industry because of the similarity of their boiling points and kinetic diameters. This study focuses on the use of pillar-layer MOF-Co(aip)(bpy)0.5 for adsorption and separation of xylene isomers. It was found that Co(aip)(bpy)0.5 exhibited a significant para-selectivity in liquid-phase competitive adsorption of xylene isomers, and the competitive separation factors reached as high as 30 for p-xylene versus m-xylene and 16 for p-xylene versus o-xylene. Desorption experiments further confirmed the preferential adsorption of p-xylene on the adsorbent. Molecular simulations and calculations revealed that the order of interaction strengths for xylene molecules and the adsorbent framework was p-xylene ≫ o-xylene ≈ m-xylene, which illustrated the selective adsorption phenomena arising from the mechanism for microscopic interactions. This work broadens the application of pillar-layer MOF materials in the field of xylene isomer adsorption and separation.

Separation of Xylene Isomers in the Anion-Pillared Square Grid Material SIFSIX-1-Cu.

Xylene isomer separation is considered one of the seven separation challenges that changed the world. In addition, the high-energy demand of xylene separation highlights the need for efficient novel adsorbents. Herein, the liquid-phase separation potential of the anion-pillared hybrid material SIFSIX-1-Cu was studied for preferential adsorption of o-xylene and m-xylene over p-xylene, which was inspired by a previous complexation crystallization method for separating m-xylene. We report detailed experimental liquid-phase adsorption experiments, yielding selectivities of 3.0 for o-xylene versus p-xylene and 2.6 for m-xylene versus p-xylene. Our theoretical calculations thus provide a reasonable explanation that the xylene adsorption selectivity is attributed to the C-H⋅⋅⋅F interaction, and the host-guest interaction order agrees with the adsorption priority: o-xylene > m-xylene > p-xylene.

Preparation of Efficient Ultraviolet-Protective Transparent Coating by Using a Titanium-Containing Hybrid Oligomer.

Ultraviolet (UV) radiation is closely related to people's lives, but excess UV exposure has led to a series of problems. UV protection technology plays a vital role in our life. The most commonly adopted UV protection technology is to use UV-absorbing materials to make protective coatings, including sunscreen cream for human skin and sunscreen coating for materials. Conventional organic UV-protective coatings have low stability and are sensitive to heat, while inorganic UV-protective coating with highly efficient UV-protective performance usually need high processing temperatures and exhibit low transparency. Here, we report a Ti-PEG-Si cross-linked inorganic-organic hybrid material, which exhibits good UV-absorbing performance. By using these UV-absorbing materials, an efficient transparent UV-absorbing coating could be easily prepared at room temperature (298 K). The UV-absorbing coating is mainly composed of titanium and silicon connected by PEG200. PEG200 as a cross-linker can improve the UV-absorption performance of the coating and increase its visible light transmittance. At the same time, the existence of PEG200 can effectively increase the stability and elasticity of the coating and maintain its mechanical properties after UV irradiation. Furthermore, the coating could maintain highly UV-protective performance and could be transparent even after thermal treatment at high temperature (973 K). From this point of view, the hybrid materials have considerable application potential in next-generation UV protective coatings, especially with their utilization in heat-sensitive substrates or under high-temperature conditions.

Oxygen-selective adsorption on high-silica LTA zeolite.

The adsorption capacity of O2 and N2 on a LTA-type zeolite can be significantly affected by the change of its Si/Al ratio. With the increase in Si/Al ratio and the decrease in the amount of Na+, the protonated high-silica LTA zeolite changes from being a N2-selective sorbent to an O2-selective sorbent to reverse the O2 and N2 selectivity.

Enhanced Propene/Propane Separation by Directional Decoration of the 12-Membered Rings of Mordenite with ZIF Fragments.

Propene/propane separation is challenging due to the very small difference in molecular sizes, boiling points and condensabilities between these molecules. Herein, we report a strategy of introducing ZIF fragments into traditional mordenite (MOR) zeolite to decorate the 12-membered ring of MOR. After decoration, the originally ineffective zeolite MOR exhibited high kinetic propene/propane selectivities (139 at 25 °C) and achieved efficient propene/propane separation. The propene/propane separation potentials of the resulting adsorbents were further confirmed by breakthrough experiments with equimolar propene/propane (50/50) mixtures.