One-pot mechanochemical synthesis to encapsulate functional guests into a metal-organic framework for proton conduction.

Through one-pot mechanochemical synthesis, a series of guests [imidazole, (aminomethyl)phosphonic acid, urea and sulfamic acid] are rapidly encapsulated into the pores of MOF NENU-3 while the MOF is formed. The synthesis of a MOF loaded with functional guests that used to take several days and require a multistep procedure can now be completed in one step within several minutes. The proton conductivities of the obtained composites increased by 2-3 orders of magnitude compared with NENU-3.

Hollow Lindqvist-like-Shaped {V6} Cluster-Based Metal-Organic Framework for the Highly Efficient Detoxification of Mustard Gas Simulant.

A polyoxovanadate-based nickel-organic framework, [Ni(bib)2]{V2O6}({V6}-MOF, bib = 1,4-bis(1H-imidazoly-1-yl)benzene), was facilely prepared under gentle hydrothermal conditions and structurally characterized. Single-crystal X-ray diffraction analysis indicates that the {V6} cluster in the {V6}-MOF is constructed of two VO5 tetragonal pyramids and four VO4 tetrahedrons via the apex sharing of O atoms, presenting a hollow Linqvist-like structure, which is different from these reported hexanuclear vanadium clusters. The {V6}-MOF not only expands the structure of polyoxovanadates (POVs) but also catalyzes the rapid detoxification of mustard gas simulant (2-chloroethyl ethyl sulfide, CEES) at 25 °C. The catalytic results were determined by means of GC, GC-MS, and 1H NMR. Using {V6}-MOF as a heterogeneous catalyst, CEES underwent catalyzed oxidation to only nontoxic product 2-chloroethyl ethyl sulfoxide (CEESO) within 40 min, and the conversion and selectivity were almost 100%. In addition, {V6}-MOF exhibits high sustainability, and no obvious reductions in conversion and selectivity are observed after five runs.

Purely inorganic frameworks based on polyoxometalate clusters with abundant phosphate groups: single-crystal to single-crystal structural transformation and remarkable proton conduction.

A pure-inorganic framework based on {P4MoV4MoVI2} clusters with rich phosphate groups has been synthesized. It underwent a single crystal to single crystal conversion in air to form a new framework with changes both in the metal valent state and coordination environment. The new framework exhibits an ultra-high proton conductivity of 1.33 × 10-2 S cm-1 at 95 °C and 98% relative humidity and excellent stability.