Ring-Shaped Polyoxometalate Built by {Mn ₄ PW ₉ } and PO ₄ Units for Efficient Visible-Light-Driven Hydrogen Evolution

Abstract

A novel mixed-valence, ring-shaped multinuclear Mn-containing polyoxometalate, [H 2 N(CH 3 ) 2 ] 15 NaH 8 -[Mn III 3 Mn IV (μ 3 -O) 3 (OAc)PO 4 (B-α-PW 9 O 34 )] 4 • 36H 2 O (1) was made and systematically characterized using various spectroscopic and computational techniques. Its polyoxoanion can be described as a tetramer made of four [Mn III 3 Mn IV (μ 3 -O) 3 (OAc) (B-α-PW 9 O 34 )] 3− ({Mn III 3 Mn IV (PW 9 )}) clusters and four PO 4 linkers. Significantly, this structurally new complex 1 can efficiently catalyze hydrogen evolution with 23 μmol H 2 gas after 12 h of visible-light irradiation using a three-component system. We propose a possible catalytic hydrogenevolving mechanism based on both experimental results and density functional theory (DFT) calculations.

{Cu8} Cluster-Sandwiched Polyoxotungstates and Their Polymers: Syntheses, Structures, and Properties

“…The Fourier transform infrared spectra and the XPS data (Figures S13b, S14b, and S15) showed that their crystal structures were maintained, highlighting the remarkable stability of the composites under photocatalytic conditions. According to the experimental results presented above and the literature, − a possible reaction mechanism for this visible light-driven H 2 evolution process is proposed (Figure S16).…”

Cluster–Nuclei Coassembled One-Dimensional Subnanometer Heteronanostructures

“…Polyoxometalate clusters (POMs) are a series of highly charged and oxygen-enriched structures with sizes between that of single atoms and conventional nanocrystals. They have attracted extensive attention in recent years because they show excellent performance in catalytic, electrocatalytic, , photocatalytic, , and medical fields. POM clusters can participate in the growth processes of nanostructures with greatly different assembly behaviors than the way of inorganic entities like metal oxide/sulfide.…”

{Ti6}/{Ti10} Wheel Cluster Substituted Silicotungstate Aggregates

“…Both possess wheel-shaped structures, and especially 2 is a rare double-wheel cluster. To our knowledge, the wheel-shaped POT species are mainly concentrated on single-wheel clusters, such as POMs with different shapes and dimensions {P 8 W 48 }, {As 4 W 40 }, {P 6 W 39 }, {Se 6 W 36 }, {Zr 6 Si 3 W 30 }, {Ti 8 Si 4 W 40 }, {Fe 48 P 16 W 96 }, {Fe 16 P 8 W 48 }, {Pd 10 Se 10 W 52 }, {Fe 8 P 4 W 40 }, {Ni 24 P 4 W 36 }, {Ru 4 As 4 W 40 }, {Mn 16 P 8 W 36 }, and so on. Clearly, double-wheel-shaped POTs have not been reported before the newly discovered 2 .…”