Tuning the release rate of volatile molecules by pore surface engineering in metal-organic frameworks

Abstract Encapsulation and controlled release of volatile molecules such as fragrances in a designed manner is important but challenging for the flavor and fragrance industry. Here, we report the tuning release of volatile molecules by postsynthetic modification of an amine-terminated metal-organic framework (MOF) MIL-101-NH2. By amidation, we obtained three MIL-101 MOFs, the trimethylacetamide-terminated TC-MIL-101, the benzamide-terminated BC-MIL-101, and the oxalic acid monoamide-terminated OC-MIL-101. All the MOFs can efficiently encapsulate volatile molecules. Moreover, we demonstrate that the release profile of volatiles can be widely tuned to sustain the release in several days to months and even over a year using different modified MIL-101 MOFs. We show that the release profiles are correlated with the binding energies between the guest volatiles and pores in MOFs. The pore diffusion and the synergistic transport are the rate-limiting step of the guest molecules from the modified MOFs.