We report a stable and semiconductive heteropolyoxotitanate of [Ti12Cr6O18(OOCC6H5)30] (denoted as POTi12Cr6), which exhibits a pronounced photocatalytic hydrogen evolution rate, photothermal effect, and photocurrent under full solar spectrum, including near-infrared (NIR) irradiation, moreover, with high stability in both acid and base aqueous solution. Crystallinity and photocatalytic activity of POTi12Cr6 remain unchanged under cycling photocatalysis tests. This work demonstrates an approach to overcome the common restriction of low stability and limited solar absorption capability in polyoxotitanate- and TiO2-based materials. The result will open up heteropolyoxotitanate as a novel type of semiconductor material for the full solar spectrum, especially NIR energy utilization including photothermal transformation, photocurrent response, and photocatalytic H2 evolution.

We present a novel strategy to improve the stability and optical absorption of polyoxotitanates (POTs) via concurrently fully carboxylate-coordinating and hetero-metal-doping, and illustrate the strategy by an indium doped hetero-polyoxotitanate (h-POT) of a [Ti12In6O18(OOCC6H5)30] (POTi12In6) nanocluster, which possesses ultrahigh stability in both acid and base aqueous solutions. The nanocluster structurally features a core–shell double wheel structure and a polar cavity. Both experiments and theoretical calculations confirm the semiconductive properties of the nanocluster. Under visible irradiation the POTi12In6 nanocluster can produce pronounced photocurrent, and reactive oxygen species for pollutant degradation. Without using any cocatalyst, POTi12In6 exhibits important visible-light-driven photocatalytic activity for H2 evolution in an aqueous system. This work could render a polyoxotitanate as a new type of visible-photoactive photocatalyst.

We present a gigantic polyoxozirconate nanocluster (Zr18O21(μ2-OH)2(OOCPh)28), involving 6, 7 and 8-coordinated Zr atoms. It exhibits visible light driven photocatalytic activity for H2 evolution. The current results could represent a prelude of polyoxozirconate-based photocatalysis.

We present a novel strategy to improve the stability and optical absorption of polyoxotitanates (POTs) via concurrently fully carboxylate-coordinating and hetero-metal-doping, and illustrate the strategy by an indium doped hetero-polyoxotitanate (h-POT) of a [Ti12In6O18(OOCC6H5)30] (POTi12In6) nanocluster, which possesses ultrahigh stability in both acid and base aqueous solutions. The nanocluster structurally features a core–shell double wheel structure and a polar cavity. Both experiments and theoretical calculations confirm the semiconductive properties of the nanocluster. Under visible irradiation the POTi12In6 nanocluster can produce pronounced photocurrent, and reactive oxygen species for pollutant degradation. Without using any cocatalyst, POTi12In6 exhibits important visible-light-driven photocatalytic activity for H2 evolution in an aqueous system. This work could render a polyoxotitanate as a new type of visible-photoactive photocatalyst.