Polyoxometalate-Complexed Indium Hydroxide: Atomically Homogeneous Impregnation via Countercation Exchange.

Metal hydroxides catalyze organic transformations and photochemical processes and serve as precursors for the oxide layers of functional multicomponent devices. However, no general methods are available for the preparation of stable water-soluble complexes of metal hydroxide nanocrystals (NCs) that might be more effective in catalysis and serve as versatile precursors for the reproducible fabrication of multicomponent devices. We now report that InIII-substituted monodefect Wells-Dawson (WD) polyoxometalate (POM) cluster anions, [α2-P2W17O61InIIIOH)]8-, serve as ligands for stable, water-soluble complexes, 1, of platelike, predominantly cubic-phase (dzhalindite) In(OH)3 NCs that after optimization contain ca. 10% InOOH. Images from cryogenic tranmsission electron microscopy reveal numerous WD ligands at the surfaces of platelike NCs, with average dimensions of 17 × 28 × 2 nm, each complexed by an average of ca. 450 InIII-substituted WD cluster anions and charge-balanced by 3600 Na+ countercations. Facilitated by the water solubility of 1, countercation exchange is used to stoichiometrically disperse ca. 1800 Cu2+ ions in an atomically homogeneous fashion around the surfaces of each NC core. The utility of this impregnation method is illustrated by using the ion-exchanged material as an electrocatalyst that reduces CO2 to CO 15 times faster per milligram of Cu than does K6Cu[P2CuII(H2O)W17O61] (control) alone. More generally, the findings point to POM complexation as a promising method for stabilizing and solubilizing reactive d-, p-, and f-block metal hydroxide NCs and for enabling their utilization as versatile components in the fabrication of functional multicomponent materials.

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.