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Metal-organic frameworks (MOFs) show remarkable potential in a broad array of applications given their physical and chemical versatility. Classical synthesis of MOFs is performed using solution chemistry at elevated temperatures to achieve reversible metal-ligand bond formation. These harsh conditions may not be suitable for chemical species sensitive to high temperature or prone to deleterious reactions with solvents. For instance, Pd(ii) is susceptible to reduction under solvothermal conditions and is not a common metal node of MOFs. We report a generic and facile mechanochemical strategy that directly incorporates a series of Pd(ii)-based heterobimetallic clusters into MOFs as metal nodes without Pd(ii) being reduced to Pd(0). Mechanochemistry features advantages of short reaction time, minimum solvent, high reaction yield, and high degree of synthetic control. Catalytic performances of lattice-confined heterobimetallic sites are examined for nitrene transfer reactions and we demonstrate that the chemoselectivity for allylic amination versus olefin aziridination is readily tuned by the identity of the first-row metal ion in Pd(ii)-based heterobimetallic clusters., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

MIL-53 represents one of the most notable metal-organic frameworks given its unique structural flexibility and remarkable thermal stability. In this study, a shaker-type ball milling method has been developed into a facile and generalizable synthetic strategy to access a family of MIL-53 type materials under ambient conditions. During the explorations of [M(OH)(fumarate)] (M = Al, Ga, and In), we report a positive correlation between the metal-ligand (M-L) bond reversibility and the size of resultant crystallites under the mechanochemical process. The more kinetically labile the M-L bond is, the larger the afforded crystallite size is.

The synthesis and characterization of two new porphyrin-based porous organic polymers (POPs) via Sonogashira cross-coupling reaction and leverage the two obtained POPs is reported for the fabrication of electrochemical aptasensors to detect kanamycin at an ultratrace level. The resultant electrochemical aptasensor demonstrates a high linear relationship with the logarithmic value of kanamycin concentration in the range 5 × 10 -5 -5 μg/L with the limit of detection of 17.6 pg/L or 36.3 fM. During the analysis of real samples from milk and river, a relative standard deviation of less than 4.39%, and good recovery values in the range 97.0-105% were obtained., (© 2024. The Author(s).)

The catalytic conversion of oleic acid to aromatics (benzene, toluene, and xylenes, BTX) over a granular H-ZSM-5/Al 2 O 3 catalyst (ϕ 1.2-1.8 mm, 10 g loading) was investigated in a continuous bench-scale fixed-bed reactor (10 g oleic acid h -1 ). A peak carbon yield of aromatics of 27.4% was obtained at a catalyst bed temperature of 550 °C and atmospheric pressure. BTX was the major aromatics formed (peak carbon yield was 22.7%), and a total BTX production of 1000 mg g -1 catalyst was achieved within a catalyst lifetime of 6.5 h for the fresh catalyst. The catalyst was deactivated due to severe coke deposition ( ca . 22.1 wt % on the catalyst). The used catalyst was reactivated by an ex situ oxidative regeneration at 680 °C in air for 12 h. The regenerated catalyst was subsequently recycled, and in total, 7 cycles of reaction-regeneration were performed. A gradual decrease in the peak carbon yield of BTX was observed with reaction-regeneration cycles ( e.g ., to 16.3% for the catalyst regenerated for 6 times). However, the catalyst lifetime was remarkably prolonged ( e.g ., >24 h), leading to a significantly enhanced total BTX production ( e.g ., 3000 mg g -1 catalyst in 24 h). The fresh, used, and regenerated catalysts were characterized by N 2 and Ar physisorption, XRD, HR-TEM-EDX, 27 Al, and 29 Si MAS ssNMR, NH 3 -TPD, TGA, and CHN elemental analysis. Negligible changes in textural properties, crystalline structure, and framework occurred after one reaction-regeneration cycle, except for a slight decrease in acidity. However, dealumination of the H-ZSM-5 framework was observed after 7 cycles of reaction-regeneration, leading to a decrease in microporosity, crystallinity, and acidity. Apparently, these changes are not detrimental for catalyst activity, and actually, the lifetime of the catalyst increases, rationalized by considering that coke formation rates are retarded when the acidity is reduced., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)