Efficient photocatalytic H2 evolution catalyzed by an unprecedented robust molecular semiconductor {Fe11} nanocluster without cocatalysts at neutral conditions

An unprecedented molecular polyanionic metal oxide cluster of eleven-Fe-III substituted antimoniotungstate Na-27[Fe-11(H2O)(14)(OH)(2)(W3O10)(2)(alpha-SbW9O33)(6)]center dot 103H(2)O(1) based on earth abundant elements has been successfully synthesized. A careful physical investigation of this molecule reveals that VB= -6.34 eV/CB= -4.39 eV, this unique physical properties ensures that 1 can be defined as a new type of nanoscale molecular semiconductor. This compound showed remarkable catalytic property for light driven H-2 evolution activity. A H-2 evolution rate of 820 mu mol h(-1) g(-1) was achieved in the presence of 1 without adding any co-catalyst at neutral condition, which is a very high rate among all polyoxotungstate photocatalysts reported thus far. Six evidences proved that 1 is a true stable molecular catalyst during the photocatalytic hydrogen evolution. (C) 2015 Elsevier Ltd. All rights reserved.