Structurally-New Hexadecanuclear Ni-Containing Silicotungstate with Catalytic Hydrogen Generation Activity

A structurally-new, carbon-free hexadecanuclear Ni-containing silicotungstate, [Ni(16)(H(2)O)(15)(OH)(9)(PO(4))(4)(SiW(9)O(34))(3)](19-), has been facilely synthesized using a one-pot, solution-based synthetic method systematically characterized by single-crystal X-ray diffraction and several other techniques. The resulting complex works as a noble-metal-free catalyst for visible-light-driven catalytic generation of hydrogen, by coupling with a [Ir(coumarin)(2)(dtbbpy)][PF(6)] photosensitizer and a triethanolamine (TEOA) sacrificial electron donor. Under minimally optimized conditions, a turnover number (TON) of 842 was achieved for TBA-Ni(16)P(4)(SiW(9))(3)-catalyzed hydrogen evolution system. The structural stability of TBA-Ni(16)P(4)(SiW(9))(3) catalyst under photocatalytic conditions was evaluated by the mercury-poisoning test, FT-IR, and DLS measurements. The photocatalytic mechanism was elucidated by both time-solved luminescence decay and static emission quenching measurements.