Bifunctional Metal-Organic Framework Functionalized by Dimethylamine Cations: Proton Conduction and Iodine Vapor Adsorption.

A metal-organic framework, {Zn3(BTB)2(µ3-OH)[(CH3)2NH2](H2O)}n (1), was synthesized based on H3BTB (1,3,5-tri(4-carboxyphenyl)benzene). An AC impedance test proves that 1 has a relatively high conductivity performance of 1.52 × 10-3 S·cm-1 at 338 K and 98% RH. The proton conductivity of the composite film 1@CS-9 (CS = chitosan) reaches 1.84 × 10-1 S·cm-1 at 328 K and 98% RH. In addition, 1 is discovered to have a good adsorption effect on iodine vapor, and the adsorption capacity reaches 726 mg·g-1. The multifunctionality caused by dimethylamine cations was investigated for the first time, which has implications for multifunctionality generated by host-guest molecules.

Designable Guest-Molecule Encapsulation in Metal-Organic Frameworks for Proton Conductivity.

Metal-organic frameworks (MOFs), as a porous frame material, exhibit considerable electrical conductivity. In recent decades, research on the proton conductivity of MOFs has made gratifying progress. In this review, the designable guest molecules encapsulated into MOFs are summarized and generalized into four types in terms of promoting proton conductive performance, and then recent progress in the promotion of proton conductivity by MOFs encapsulating guest molecules is discussed. The existing challenges and prospects for the development of this strategy for promoting MOFs' proton conductivity are also listed.

Dual-Functional Coordination Polymer with High Proton Conductivity and a Low-Detection-Limit Fluorescent Probe.

A coordination polymer with dual functions of high proton conductivity and highly sensitive fluorescent sensors demonstrates a great application potential. In this work, a cadmium-based coordination polymer (denoted as CP 1) with hydrothermal stability was synthesized. The abundant coordination water, lattice water, and amino groups make an extended hydrogen-bonding pathway for efficient proton migration, which endows CP 1 with the highest proton conductivity of 2.41 × 10-3 S·cm-1 at 353 K and 98% RH. Especially, the proton conductivity of the chitosan (CS) hybrid membrane containing CP 1 reaches a maximum value of 2.62 × 10-2 S·cm-1 under 343 K and 98% RH, which increases almost 7 times higher than that of the pure CS membrane due to the host-guest collaboration. Furthermore, luminescence studies revealed that CP 1 is a high-sensitivity and good-selectivity fluorescent probe for the detection of trace amounts of l-histidine with a lowest detection limit of 1.0 × 10-8 M.

Promotion of Proton Conductivity by Encapsulation of Metal-Organic Polyhedra in Metal-Organic Frameworks.

A Zr-based metal-organic polyhedron (MOP) was self-assembled in a porous MOF host, DUT-68, successfully to synthesize MOP-1@DUT-68. The MOP guest (MOP-1) has a diameter of about 20 Å, larger than that of the square windows (pore sizes of ∼14 Å) of DUT-68 but smaller than that of the rhombicuboctahedral cage (27.7 Å), which means that the migration and leaching of MOP-1 could be effectively prohibited if MOP-1 is encapsulated in the MOF's cavities. The proton conductivity of MOP-1@DUT-68 is 1.14×10-3  S cm-1 (at 80 °C under 98 % relative humidity), which is three orders of magnitude higher than that of DUT-68. Compared with MOP-1⊂DUT-68, which was synthesized by impregnation, MOP-1@DUT-68 is more prone to form faster proton-conduction pathways and thus provides higher proton conductivity.

Dual-functional coordination polymers with high proton conduction behaviour and good luminescence properties.

Two coordination polymers, [M(5-hip)(H2O)3]n (M = Cd2+ (1), Zn2+ (2), 5-hip = 5-hydroxyisophthalic acid), have been synthesized under hydrothermal conditions. The crystal structure reveals that complexes 1 and 2 have 1D chain structures by the coordination of metal ions and 5-hip. 1D chains are connected by hydrogen bonds to form a 3D structure. AC impedance analysis shows that the proton conductivity of complexes 1 and 2 comes up to 1.58 × 10-3 S cm-1 (98%RH, 343 K) and 5.27 × 10-4 S cm-1 (98%RH, 353 K), respectively. To further improve the proton conductivity, a hybrid membrane was prepared by the solution casting method with complexes as fillers and sulfonated polyether ether ketone (SPEEK) as the organic matrix. The proton conductivity of hybrid membranes 1@SPEEK-5 and 2@SPEEK-5 is 1.97 and 1.58 times higher than that of pure SPEEK membranes, respectively. Furthermore, the two complexes are excellent fluorescent sensors, which could detect Cr2O72- in aqueous solution with high sensitivity and selectivity. Both of them have low detection limits for Cr2O72- in aqueous solution, where the detection limit of complex 1 is 0.8 µM and that of complex 2 is 1 µM. The above work demonstrates that the two complexes are dual-functional materials with high proton conduction and good fluorescence properties.

A dual-functional MOF for high proton conduction and sensitive detection of ascorbic acid.

A new metal-organic framework (MOF), [Eu2(HBDPP)2(H2O)2(DMF)2](H2O)2 (H4BDPP = 3,5-bis(3,5-dicarboxylphenyl) pyridine; DMF = N,N-dimethylformamide) (Eu-MOF), has been successfully synthesized under solvothermal conditions. A 1D chain was formed by the adjacent Eu2(COO)24+ dinuclear cluster and HBDPP3-, and further connected by HBDPP3- to form an infinitely extended 3D structure. In order to further improve the proton conductivity of the Eu-MOF, imidazole was encapsulated in its pores to form a composite material named Im@Eu-MOF. AC impedance analysis shows that the highest proton conductivity of the Im@Eu-MOF reaches up to 4.53 × 10-4 S cm-1 at 348 K and 98% RH, which is about 10 times higher than that of the Eu-MOF. In addition, the Eu-MOF can be considered an excellent luminescence-based sensor with a high sensitivity and low detection limit (0.1 µM) for the detection of trace amounts of ascorbic acid.