Zheng-Fang Tian

A series of metal–organic frameworks based on 5-(4-pyridyl)-isophthalic acid: selective sorption and fluorescence sensing

Solvothermal reactions of 5-(4-pyridyl)-isophthalic acid (H2pbdc) and transition-metal centers (Ni2+/Co2+/Zn2+) in the presence (or absence) of N-auxiliary 4,4′-bis(1-imidazolyl)biphenyl (bimb) ligand produce [Ni2(pbdc)2(μ2-H2O)(H2O)2·(DMA)2.7]n (DMA = N,N′-dimethylacetamide, 1), [Ni12(pbdc)12(μ2-H2O)6(py)2(H2O)8(DMA)2·(H2O)5·(DMA)9]n (2), [Co2(pbdc)2(bimb)2·(bimb)0.5·(H2O)4·(DMF)0.25]n (3) and [Zn(pbdc)(bimb)·(H2O)]n (4), which exhibit structural diversity. Both compounds 1 and 2 display a uninodal 8-connected 3D tsi net, but feature different crystal systems and space groups from each other. Compound 3 adopts a 2-fold interpenetrating binodal (3,5)-connected 3D hms net and compound 4 features a rare 2-fold interpenetrating binodal (3,4)-connected 3D fsx architecture. In particular, activated 3 shows high-efficiency for the selective sorption of small molecules, including CO2 over N2 and CH4, H2 over N2, as well as alcohols from water. More importantly, 4 represents the first report on a MOF as a promising luminescent probe for detecting pesticides, and also the very first example for detecting both pesticides and solvent molecules simultaneously.

Proton Conductance of a Superior Water-Stable Metal–Organic Framework and Its Composite Membrane with Poly(vinylidene fluoride)

Proton-exchange membranes (PEMs) as separators have important technological applications in electrochemical devices, including fuel cells, electrochemical sensors, electrochemical reactors, and electrochromic displays. The composite membrane of a proton-conducting metal-organic framework (MOF) and an organic polymer combines the unique physical and chemical nature of the polymer and the high proton conductivity of the MOF, bringing together the best of both components to potentially fabricate high-performance PEMs. In this study, we have investigated the proton-transport nature of a zirconium(IV) MOF, MOF-808 (1). This superior-water-stability MOF shows striking proton conductivity with σ = 7.58 × 10-3 S·cm-1 at 315 K and 99% relative humidity. The composite membranes of 1 and poly(vinylidene fluoride) (PVDF) have further been fabricated and are labeled as 1@PVDF-X, where X represents the mass percentage of 1 (as X%) in 1@PVDF-X and X = 10-55%. The composite membranes exhibit good mechanical features and durability for practical application and a considerable proton conductivity of 1.56 × 10-4 S·cm-1 in deionized water at 338 K as well. Thus, the composite membranes show promising applications as alternative PEMs in diverse electrochemical devices.

Water assisted high proton conductance in a highly thermally stable and superior water-stable open-framework cobalt phosphate

Proton-conducting materials show important technological applications as key components in energy conversion, electrochemical sensing and electrochromic devices; the exploration for new types of proton-conducting materials is crucial for the development of efficient electrochemical devices. In this study, we investigated the proton transport nature of an inorganic-organic hybrid crystal of open-framework cobalt phosphate, (C2N2H10)0.5CoPO4. The structure of the hybrid crystal consists of the [CoPO4]-∞ anionic framework, and the proton carriers, H2en2+ cations (en = ethylenediamine), are located in the pores to compensate the negative charges of the inorganic framework. The open-framework is thermally stable up to 653 K (380 °C) at least, and also shows superior water stability. The open-framework exhibits negligible conductance in an anhydrous environment even at 473 K; however, there is evident water-assisted proton conduction. The conductivity reaches 2.05 × 10-3 S cm-1 at 329 K and 98% RH. Such high proton conductivity can compete with numerous state-of-the-art MOFs/PCPs-based proton conductors, and this material has promising applications in diverse electrochemical devices.

Open-Framework Chalcogenide Showing Both Intrinsic Anhydrous and Water-Assisted High Proton Conductivity

Proton-conducting materials have attracted increasing interest because of the promising technological applications as key components in various electrochemical devices. It is of great significance for technique application to seek superior proton-conducting materials, operating under both anhydrous and humidified conditions in a wide temperature range. Herein we demonstrate the proton conductance of an open-framework chalcogenide, (CH3NH3)2Ag4Sn3S8 (1), and the postsynthesis product 2 achieved by doping hydrochloric acid into 1. Hybrid 2 displays both intrinsic anhydrous and water-assisted high proton conductance, with σ = 1.87 × 10-4 S·cm-1 at 463 K under N2 atmosphere and 1.14 × 10-3 S·cm-1 at 340 K and 99% relative humidity, and these conductivities are comparable to that in the efficient metal-organic frameworks-based proton-conducting materials. Moreover, hybrid 2 shows excellent thermal stability and long-term stability of proton conduction.

Both Dielectrics and Conductance Anomalies in an Open-Framework Cobalt Phosphate

Switchable conducting or dielectric materials, as the key component, show important technological applications in modern electrical and electronic devices, including data communication, phase shifters, varactors, and rewritable optical data storage. To explore new types of switchable conducting or dielectric materials could significantly accelerate the development of efficient electrical and electronic devices. Herein we present the first example of switchable conducting and dielectric material, which is based on an open-framework phosphate, (C2N2H10)0.5CoPO4. A reversible isostructural phase transition occurs at ∼348 K in this open-framework phosphate, to give both dielectrics and conductance anomaly around the critical temperature of phase transition. This study will provide a roadmap for searching new switchable conducting or dielectric materials as well as new applications of open-framework phosphates.

A high temperature reversible phase transition in a supramolecular complex of 15-crown-5 with tetraphenylboron sodium

A supramolecular crystal, [Na(15-crown-5)][BPh4] (1), (15-crown-5 = 1,4,7,10,13-pentaoxacyclopentadecane, NaBPh4 = sodium tetraphenylboron), has been obtained by mixing the ethanol solution of 15-crown-5 and NaBPh4 in the molar ratio of 1 : 1. The crystal structure was determined at 293 K, revealing that two [Na(15-crown-5)]+ cations form a supramolecular dimer via sharing one side-edge of coordination pentagonal pyramids; also, there are significant H-bonding interactions between anions and supramolecularly dimeric cations. Differential scanning calorimetry (DSC) showed that 1 undergoes a reversible first-order phase transition at ca. 391 K (Tc) upon heating, with a thermal hysteresis of 19 K. ΔH and ΔS were estimated to be 6.9 kJ mol−1 and 17.7 J mol−1 K−1, respectively, in the heating run. The variable-temperature powder X-ray diffraction and dielectric spectra were collected, and both disclosed no significant difference between the low- and high-temperature phases. These results suggest that the phase transition is an ordered–disordered type, which probably involves the change of anion configuration.

Extra Water- and Acid-Stable MOF-801 with High Proton Conductivity and Its Composite Membrane for Proton-Exchange Membrane

Proton-exchange membranes (PEMs), characterized by selectively permitting the transfer of protons and acting as a separator in electrochemical devices, have attracted immense attention. The composite membrane, fabricated from organic polymer matrix and high proton-conducting metal-organic framework (MOF), integrates the excellent physical and chemical performances of the polymer and MOF, achieving collective properties for good-performance PEMs. In this study, we demonstrate that MOF-801 shows remarkable proton conductance with σ = 1.88 × 10-3 S cm-1 at 298 K and 98% relative humidity (RH), specifically, together with extra stability to hydrochloric acid or diluting sodium hydroxide aqueous solutions and boiling water. Furthermore, the composite membranes (denoted MOF-801@PP- X, where X represents the mass percentage of MOF-801 in the membrane) have been fabricated using the sub-micrometer-scale crystalline particles of MOF-801 and blending the poly(vinylidene fluoride)-poly(vinylpyrrolidone) matrix, and these PEMs display high proton conductivity, with σ = 1.84 × 10-3 S cm-1 at 325 K 98% RH. A composite membrane as PEM was assembled into H2/O2 fuel cell for tests, indicating that these membrane materials have vast potential for PEM application on electrochemical devices.