Directional Engraving within Single Crystalline Metal–Organic Framework Particles via Oxidative Linker Cleaving

Abstract

An oxidative linker cleaving (OLC) process was developed for surgical manipulation of the engraving process within single crystalline MOFs particles. The strategy relies on selective degradation of 2,5-dihydroxyterephthalic acid linker into small molecular fragments by oxidative ring-opening reactions, resulting in controllable scissoring of framework. By regulation of the generation and diffusion of oxidative species, the core MOFs will undergo divergent etching routes, producing a series of single crystalline hollow and yolk–shell MOF structures. In addition, the OLC process can be initiated and localized around the pre-embedded Pd NPs through on-site catalytic generation of oxidative species, leading to solitary confinement of multiple NPs within one single crystalline MOF particle, namely, a multi-yolk–shell structure. This unique architecture can effectively protect NPs from agglomeration while realizing size selective catalysis at the same time.

Hierarchically structured porous materials: synthesis strategies and applications in energy storage

“…Metal-organic frameworks (MOFs) is a new family of porous materials with regular pore structures formed by the connection of metal ions and organic ligands [ 120–123 ]. Recently, high-orientation etching of MOF particles can be realized to fabricate hollow MOFs through precise engraving by selective leaching [ 124 ]. It can greatly improve the chemical kinetics of these materials, which provides new ideas to prepare the hierarchical MOFs with more complex morphologies in the future.…”

Shining Light on Porous Liquids: From Fundamentals to Syntheses, Applications and Future Challenges

“…This is the first report of PLs based on mesoporous pore generators (Figure 13c). Before this study, some studies of grafting polymers onto MOF surfaces had been reported by Li et al [122][123][124][125][126][127][128][129][130] For example, through coordination of the carboxylate groups with carboxylate moieties were anchored onto MOF surfaces. [121] Next, dense polymer chains were formed by surface-initiated ATRP (SI-ATRP) reaction by adding cross-linking agents and monomers.…”

When hollow multishelled structures (HoMSs) meet metal–organic frameworks (MOFs)

“…6). 69 In contrast to the selective etching of different MOFs, the fabrication of hollow MOFs starting with a single composition precursor is quite constructive, [70][71][72] aer determining that the inhomogeneity in the MOF is due to the unevenly distributed defects. Normally, the core of the as-synthesized materials has more defects, because of the rapid nucleation and growth at the initial stage 73 and the defect-rich part was less stable than the well-crystallized part.…”