Substrate‐supported metal–organic frameworks (MOFs) films are desired to realize their potential in practical applications. Herein, a novel substrate‐seeding secondary‐growth strategy is developed to prepare composites of uniform MOFs films on aerogel walls. Briefly, the organic ligand is “pre‐seeded” onto the aerogel walls, and then a small amount of metal‐ion solution is sprayed onto the prepared aerogel. The sprayed solution diffuses along the aerogel walls to form a continuous thin layer, which confines the nucleation reaction, promoting the formation of uniform MOFs films on the aerogel walls. The whole process is simple in operation, highly efficient, and eco‐friendly. The resulting hierarchical MOFs/aerogel composites have abundant accessible active sites and enable excellent mass transfer, which endows the composite with outstanding catalytic activity and stability in both liquid‐phase CO2 cycloaddition and electrochemical oxygen evolution reaction (OER) process.
Bimetallic organic frameworks (Bi-MOFs) have been recognized as one of the most ideal precursors to construct metal oxide semiconductor (MOS) composites, owing to their high surface area, various chemical structures, and easy removal of the sacrificial MOF scaffolds through calcination. Herein, we synthesized Zn/Ni Bi-MOF for the first time via a facile ion exchange postsynthetic strategy, formed a three-dimensional framework consisting of infinite one-dimensional chains that is unattainable through the direct solvothermal approach, and then transformed the Zn/Ni Bi-MOF into a unique ZnO/NiO heterostructure through calcination. Notably, the obtained sensor based on a ZnO/NiO heterostructure exhibits an ultrahigh response of 280.2 toward 500 ppm n-propanol at 275 °C (17.2fold enhancement compared with that of ZnO), remarkable selectivity, and a limit of detection of 200 ppb with a notable response (2.51), which outperforms state-of-the-art n-propanol sensors. The enhanced n-propanol sensing properties may be attributed to the synergistic effects of several points including the heterojunction at the interface between the NiO and ZnO nanoparticles, especially a one-dimensional chain MOF template structure as well as the chemical sensitization effect of NiO. This work provides a promising strategy for the development of a novel Bi-MOF-derived MOS heterostructure or homostructure with well-defined morphology and composition that can be applied to the fields of gas sensing, energy storage, and catalysis.
This study investigated the impact of bromide on the formation of N-nitrosamines during chlorination and chloramination, and tried to identify the reactive intermediates responsible for variations in the yield of N-nitrosamines. As an intermediate of the reaction between bromide and HOCl, bromine chloride (BrCl) may improve the yield of N-nitrosodimethylamine (NDMA) formation. But increasing the amount of bromide added would result in BrCl being converted into HOBr, which is a weaker oxidant than HOCl. This would result in less nitrite being formed, leading to a decreased yield of NDMA via the nitrosation pathway. When NH4+, was present with the bromide during chlorination, both the rate of formation and yield of N-nitrosamines were improved markedly by highly reactive bromamines. Interestingly, bromide had an inhibitory effect on NDMA formation during the chloramination process when tertiary alkylamines, such as 3-(Dimethylaminomethyl) indole (DMAI) and trimethylamine (TMA), were used as precursors. This phenomenon provides indirect evidence for the hypothesis that the pathway of NDMA formation using tertiary amines with DMA groups is different from that of NDMA formation using secondary alkylamines.
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