Emergence of Visible-Light Water Oxidation Upon Hexaniobate-Ligand Entrapment of Quantum-Confined Copper-Oxide Cores.

The formation of small 1 to 3 nm organic-ligand free metal-oxide nanocrystals (NCs) is essential to utilization of their attractive size-dependent properties in electronic devices and catalysis. We now report that hexaniobate cluster-anions, [Nb6 O19 ]8- , can arrest the growth of metal-oxide NCs and stabilize them as water-soluble complexes. This is exemplified by formation of hexaniobate-complexed 2.4-nm monoclinic-phase CuO NCs (1), whose ca. 350 Cu-atom cores feature quantum-confinement effects that impart an unprecedented ability to catalyze visible-light water oxidation with no added photosensitizers or applied potentials, and at rates exceeding those of hematite NCs. The findings point to polyoxoniobate-ligand entrapment as a potentially general method for harnessing the size-dependent properties of very small semiconductor NCs as the cores of versatile, entirely-inorganic complexes.

A Zr-Based Metal-Organic Framework with a DUT-52 Structure Containing a Trifluoroacetamido-Functionalized Linker for Aqueous Phase Fluorescence Sensing of the Cyanide Ion and Aerobic Oxidation of Cyclohexane.

A zirconium (Zr) metal-organic framework having a DUT-52 (DUT stands for Dresden University of Technology) structure with face-centered cubic topology and bearing the rigid 1-(2,2,2-trifluoroacetamido) naphthalene-3,7-dicarboxylic acid (H2NDC-NHCOCF3) ligand was prepared, and its solid structure was characterized with the help of the X-ray powder diffraction (XRPD) technique. Other characterization methods like thermogravimetric analysis (TGA) and Fourier transform infrared (FT-IR) spectroscopy were applied to verify the phase purity of the compound. In order to get the solvent-free compound (1'), 1 was stirred with methanol for overnight and subsequently heated at 100 °C overnight under vacuum. As-synthesized (1) and activated (1') compounds are thermally stable up to 300 °C. The Brunsuer Emmett-Teller (BET) surface area of 1' was found to be 1105 m2 g-1. Fluorescence titration experiments showed that 1' exhibits highly selective and sensitive fluorescence turn-on behavior toward cyanide (CN-) anion. The interference experiments suggested that other anions did not interfere in the detection of CN-. Moreover, a very short response time (2 min) was shown by probe 1' for CN- detection. The detection limit was found to be 0.23 µM. 1' can also be effectively used for CN- detection in real water samples. The mechanism for the selective detection of CN- was investigated systematically. Furthermore, the aerobic oxidation of cyclohexane was performed with 1' under mild reaction conditions, observing higher activity than the analogous DUT-52 solid under identical conditions. These experiments clearly indicate the benefits of hydrophobic cavities of 1' in achieving higher conversion of cyclohexane and cyclohexanol/cyclohexanone selectivity. Catalyst stability was proved by two consecutive reuses and comparing the structural integrity of 1' before and after reuses by the XRPD study.