期刊
ADVANCED THEORY AND SIMULATIONS
卷 1, 期 2, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/adts.201700015
关键词
boronic ester linkage; covalent organic frameworks; density functional theory; hydrolytic reactions; potential energy surface
资金
- Army Research Office Multidisciplinary University Research Initiative (MURI) program [W911NF-15-1-0447]
- Army Research Office [W911NF-17-1-0339]
- King Abdullah University of Science and Technology
- National Natural Science Foundation of China [21403037]
The stability of covalent organic frameworks (COFs) is essential to their applications. However, the common boronate ester-linked COFs are susceptible to attack by nucleophiles (such as water molecules) at the electron-deficient boron sites. To provide an understanding of the hydrolytic stability of the representative boronate ester-linked COF-5 and of the associated hydrolysis mechanisms, density functional theory (DFT) calculations were performed to characterize the hydrolysis reactions of the molecule formed by the condensation of 1,4-phenylenebis(boronic acid) (PBBA) and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) monomers; two cases were considered, one dealing with the freestanding molecule and the other with the molecule interacting with COF layers. It was found that the boronate ester (B-O) bond dissociation, which requires one H2O molecule, has a relatively high energy barrier of 22.3 kcal mol(-1). However, the presence of an additional H2O molecule significantly accelerates hydrolysis by reducing the energy barrier by a factor of 3. Importantly, the hydrolysis of boronate ester bonds situated in a COF environment follows reaction pathways that are different and have increased energy barriers. These results point to an enhanced hydrolytic stability of COF-5 crystals.
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