Two nickel-added poly(polyoxometalate)s built of Keggin-type {NiPW} and Anderson-type NiWO WO/SbO bridges and Ni-O-W linkages with efficient hydrogen evolution activity.

Two Ni-added poly(polyoxometalate)s built of Keggin-type {NiPW} and Anderson-type NiWO units WO/SbO bridges and Ni-O-W linkages, NaH[Ni(enMe)][(SbO)(NiWO)-{NiO(OH)(enMe)(HO)(WO)(B-α-PWO)}]·39HO (1) and H[Ni(en)(HO)][Ni(en)(HO)][Ni-(enMe)(HO)][(SbO)(NiWO){NiO(OH)(en)(enMe)(HO)(WO)}-{NiO(OH)(en)(HO)(WO)}(B-α-PWO)]·45HO (2), have been hydrothermally synthesized and characterized, in which the {Ni(WO)(PW)} subunit was obtained by the synergistic directing effect of 2 lacunary PWO (PW) fragments and further linked by a central Anderson-type (SbO)(NiWO) bridge. Both compounds represent the first example of Ni-added polyoxometalates (POMs) simultaneously based on Keggin-type and Anderson-type POM components. Photocatalytic studies revealed that 2 can work as an efficient heterogeneous catalyst towards a light-driven H evolution reaction, achieving a hydrogen evolution rate of as high as 19 214 μmol g h (TON = 1500), which is superior to most of the reported POM-based heterogeneous catalysts.