Dual-Intermetallic Heterostructure on Hierarchical Nanoporous Metal for Highly Efficient Alkaline Hydrogen Electrocatalysis.

Constructing well-defined active multisites is an effective strategy to break linear scaling relationships to develop high-efficiency catalysts toward multiple-intermediate reactions. Here, dual-intermetallic heterostructure composed of tungsten-bridged Co3W and WNi4 intermetallic compounds seamlessly integrated on hierarchical nanoporous nickel skeleton is reported as a high-performance nonprecious electrocatalyst for alkaline hydrogen evolution and oxidation reactions. By virtue of interfacial tungsten atoms configuring contiguous multisites with proper adsorptions of hydrogen and hydroxyl intermediates to accelerate water dissociation/combination and column-nanostructured nickel skeleton facilitating electron and ion/molecule transportations, nanoporous nickel-supported Co3W-WNi4 heterostructure exhibits exceptional hydrogen electrocatalysis in alkaline media, with outstanding durability and impressive catalytic activities for hydrogen oxidation reaction (geometric exchange current density of ≈6.62 mA cm-2) and hydrogen evolution reaction (current density of ≈1.45 A cm-2 at overpotential of 200 mV). Such atom-ordered intermetallic heterostructure alternative to platinum group metals shows genuine potential for hydrogen production and utilization in hydroxide-exchange-membrane water electrolyzers and fuel cells.

A novel MOF with mesoporous cages for kinetic trapping of hydrogen.

A stable MOF, assigned PCN-105, with two types of mesoporous cages, has been prepared by using a new multidentate flexible ligand with amine functional groups, and PCN-105 exhibits a marked N(2), O(2), Ar and H(2) hysteretic behaviour.

Functional mesoporous metal-organic frameworks for the capture of heavy metal ions and size-selective catalysis.

By using Zn(4)O(CO(2))(6) as secondary building units (SBUs) and two extended ligands containing amino functional groups, TATAB and BTATB (TATAB = 4,4',4''-s-triazine-1,3,5-triyltri-p-aminobenzoate and BTATB = 4,4',4''-(benzene-1,3,5-triyltris(azanediyl))tribenzoate), two isostructural mesoporous metal-organic frameworks (MOFs) with cavities up to 2.73 nm, designated as PCN-100 and PCN-101 (PCN represents porous coordination network), have been synthesized. N(2) sorption isotherms of both PCN-100 and -101 showed typical type IV behavior, indicating their mesoporous nature. The TATAB ligand that comprises PCN-100 was employed to capture heavy metal ions (Cd(II) and Hg(II)) by constructing complexes within the pores with a possible coordination mode similar to that found in aminopyridinato complexes. This reveals that mesoporous materials such as PCN-100 can be applied in the elimination of heavy metal ions from waste liquid. In addition, both PCNs-100 and -101 exhibit size-selective catalytic activity toward the Knoevenagel condensation reaction.

A novel microporous MOF with the capability of selective adsorption of xylenes.

A novel 3D metal-organic framework (MOF) with 2D rhombic channels was synthesized for selective adsorption of p-xylene from xylene isomers by acting as a molecular sieve.

Unprecedented marriage of a cationic pentanuclear cluster and a 2D polymeric anionic layer based on a flexible tripodal ligand and a Cu(II) ion.

The anionic CdI(2)-type topological net, [Cu(2)(tci)(2)](2-), and the pentanuclear copper cluster cation [Cu(5)(tci)(2)(OH)(2)(H(2)O)(8)](2+) [tci = tris(2-carboxyethyl)isocyanurate] form a complementary 3D supramolecular framework. Interestingly, there exist centrosymmetric cyclic (H(2)O)(18) clusters in the cavities.

Porous coordination polymers with zeolite topologies constructed from 4-connected building units.

Two novel 3D coordination polymers, Cd(CTC)(H2O).(H2PIP)(0.5)(H2O) (1) with zeolite ABW topology and Cd(CTC).(HIPA) (2) with zeolite BCT topology, have been synthesized by constructing inorganic and organic 4-connected building units and using the organic bases as templates, and the frameworks of and not only expand the original structures of zeolites ABW and BCT, but also exhibit significant advantages over them in terms of thermal stability, ion exchange and adsorption.

Microporous metal-organic framework constructed from heptanuclear zinc carboxylate secondary building units.

A novel, three-dimensional, noninterpenetrating microporous metal-organic framework (MOF), [Zn7O2(pda)5(H2O)2]5 DMF4 EtOH 6 H2O (1) (H2PDA=p-phenylenediacrylic acid, DMF=N,N-dimethylformamide, EtOH=ethanol), was synthesized by constructing heptanuclear zinc carboxylate secondary building units (SBUs) and by using rigid and linear aromatic carboxylate ligands, PDA. The X-ray crystallographic data reveals that the seven zinc centers of 1 are held together with ten carboxylate groups of the PDA ligands and four water molecules to form a heptametallic SBU, Zn7O4(CO2)10, with dimensions of 9.8 x 9.8 x 13.8 A3. Furthermore, the heptametallic SBUs are interconnected by PDA acting as linkers, thereby generating an extended network with a three-dimensional, noninterpenetrating, intersecting large-channel system with spacing of about 17.3 A. As a microporous framework, polymer 1 shows adsorption behavior that is favorable towards H2O and CH3OH, and substantial H2 uptake. In terms of the heptanuclear zinc carboxylate SBUs, polymer 1 exhibits interesting photoelectronic properties, which would facilitate the exploration of new types of semiconducting materials, especially among MOFs containing multinuclear metal carboxylate SBUs.