Zirconium-based metal-organic frameworks and their roles in electrocatalysis.

Due to their exceptional chemical stability in water and high structural tunability, zirconium(IV)-based MOFs (Zr-MOFs) have been considered attractive materials in the broad fields of electrocatalysis. Numerous studies published since 2015 have attempted to utilise Zr-MOFs in electrocatalysis, with the porous framework serving as either the active electrocatalyst or the scaffold or surface coating to further enhance the performance of the actual electrocatalyst. Herein, the roles of Zr-MOFs in electrocatalytic processes are discussed, and some selected examples reporting the applications of Zr-MOFs in various electrocatalytic reactions, including several studies from our group, are overviewed. Challenges, limitations and opportunities in using Zr-MOFs in electrocatalysis in future studies are discussed.

Immobilization of europium and terbium ions with tunable ratios on a dispersible two-dimensional metal-organic framework for ratiometric photoluminescence detection of D2O.

A two-dimensional zirconium-based metal-organic framework (2D Zr-MOF), ZrBTB (BTB = 1,3,5-tri(4-carboxyphenyl)benzene), is used as a platform to simultaneously immobilize terbium ions and europium ions with tunable ratios on its hexa-zirconium nodes by a post-synthetic modification. The crystallinity, morphology, porosity and photoluminescence (PL) properties of the obtained 2D Zr-MOFs with various europium-to-terbium ratios are investigated. With the energy transfer from the excited BTB linker to the installed terbium ions and the energy transfer from terbium ions to europium ions, a low loading of immobilized europium ions and a high loading of surrounding terbium ions in the 2D Zr-MOF result in the optimal PL emission intensities of europium; this phenomenon is not observable for the physical mixture of both terbium-installed ZrBTB and europium-installed ZrBTB. The role of installed terbium ions as efficient mediators for the energy transfer from the excited BTB linker to the installed europium ion is confirmed by quantifying PL quantum yields. As a demonstration, these materials with modulable PL characteristics are applied for the ratiometric detection of D2O in water, with the use of the stable emission from the BTB linker as the reference. With the strong emission of immobilized europium ions and the good dispersity in aqueous solutions, the optimal bimetal-installed ZrBTB, Eu-Tb-ZrBTB(1 : 10), can achieve the sensing performance outperforming those of the terbium-installed ZrBTB, europium-installed ZrBTB and the physical mixture of both.