Multivariate metal−organic frameworks (MTV-MOFs) have drawn much attention in recent years for their promising applications in many fields of chemistry and materials. Constructing functional MOFs from multiple components for electrochemical water is crucial to high performance renewable energy storage and conversion devices. In this work, a series of bitmetallic-, trimetallic-, and tetrametallic-MOF-74/NFs were grown in situ on nickel foam (NF) by a facile solvothermal route. Specifically, the optimized FeCoMnNi-MOF-74/NF with a multilevel and hollow nanostructure was successfully fabricated and used as highly efficient bifunctional electrocatalysts for water splitting. It exhibited an ultralow overpotential of 250 and 108 mV to achieve the current density of 50 and 10 mA cm −2 , along with the relatively small Tafel slope of 41.28 and 72.89 mV dec −1 for OER and HER in 1 M KOH, respectively. It is superior to other multimetallic-MOF-74 composites at the same condition and also surpasses the benchmark of commercial noble-metal catalysts as well. As a result, a low cell voltage of ca. 1.62 V was obtained at a current density of 10 mA cm −2 , when tetrametallic FeCoMnNi-MOF-74/NF is employed as both anode and cathode electrodes for the real water splitting. The present work potentially provides a new insight into prospecting and designing multivariate MOFs as a promising material for efficient electrocatalysis in the practical application.

The hierarchical CuOx@Co3O4catalyst shows notable OER and HER activities in an alkaline environment.

Self-assembly reactions of copper (II) ions, dicarboxylate (adipate or terephthalate) and terminal ligands (4,4′-bipyridine or phenanthroline) yielded three hydroxy-bridged Cu(II) cluster complexes: [Cu(phen 8 H 4 O 4 ) 2 • 6H 2 O (2) and [Cu 6 (bpy) 6 (OH) 6 (H 2 O) 2 ] • (C 6 H 8 O 4 ) 3 • 23H 2 O (3) (phen ) phenanthroline, bpy ) 2,2′-bipyridine, C 8 H 6 O 4 ) terephthalic acid, C 6 H 10 O 4 ) adipic acid). Single crystal X-ray diffraction analyses reveal that complex 1 is a discrete dinuclear Cu 2 O 2 motif, 2 presents a discrete chairlike tetranuclear copper(II) Cu 4 O 4 core formed by two Cu 2 O 2 units, and 3 assumes a discrete hexameric copper(II) Cu 6 O 6 cluster consisting of three Cu 2 O 2 units. The polynuclear structures are generated from the Cu(II) ions linked by the µ 2 -and/or µ 3 -OH groups. In 1-3, all Cu(II) ions show square pyramidal coordination geometry, and the dicarboxylate ions act as counteranions to keep the whole structure neutral. Thermogravimetric analyses (TGA) and magnetic properties of 1-3 were studied, respectively.

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